JPWO2007148439A1 - Polymerizable composition and resin, optical component and lens using the same - Google Patents

Abstract

The polymerizable composition contains a compound represented by the following general formula (1) and a bluing agent. (In the following general formula (1), M represents a metal atom, X1 and X2 each independently represent a sulfur atom or an oxygen atom, R1 represents a divalent organic group, and m represents an integer of 0 or 1 or more. P represents an integer of 1 to n, n represents the valence of the metal atom M, Y represents each independently an inorganic or organic residue, and when np is 2 or more, Y represents And may form a ring containing a metal atom M.)

Description

  The present invention relates to a polymerizable composition, a resin obtained by polymerizing the polymerizable composition, and an optical component and a lens made of the resin.

  Inorganic glass is used in a wide range of fields as a transparent material because it is excellent in various properties such as excellent transparency and small optical anisotropy. However, there are disadvantages such as being heavy and easily damaged, and having poor productivity when a product is obtained by molding, and transparent organic polymer materials (optical resins) are used as a material to replace inorganic glass. Optical parts obtained from such optical resins include, for example, plastic lenses such as eyeglass lenses for correcting vision and lenses for photographing devices such as digital cameras, and are being put into practical use and are becoming popular. In particular, eyeglass lenses for correcting visual acuity are widely used taking advantage of features such as being lighter and harder to break than inorganic glass lenses, and capable of being dyed and rich in fashion.

  Conventionally, a cross-linkable resin (commonly referred to as a DAC resin) obtained by casting polymerization of diethylene glycol bisallyl carbonate under heating has been put to practical use as an optical resin used in spectacle lenses, and has good transparency and heat resistance. Because of its low chromatic aberration, it has been most frequently used in general-purpose vision correction plastic spectacle lens applications. However, since the refractive index is low (1.50), the center thickness and peripheral thickness (edge thickness) of the plastic lens are increased, and there are problems such as inferior wearing feeling and fashionability, and these problems can be solved. A high refractive index resin for plastic lenses was demanded and developed.

  In the flow, polythiourethane containing sulfur atoms obtained by cast polymerization of a diisocyanate compound and a polythiol compound is excellent in transparency and impact resistance, and has a high refractive index (1.6 to 1. It has been used in applications such as a thin, lightweight, high-quality plastic eyeglass lens for correcting eyesight, which achieves excellent characteristics such as 7) and relatively low chromatic aberration.

  On the other hand, it is obtained by polymerizing a compound having an episulfide group (Patent Document 1 and Patent Document 2) or a compound having a thietane group (Patent Document 3) in the pursuit of an optical resin having a higher refractive index. Some proposals such as a resin obtained by polymerizing a transparent resin or a Se-containing compound (Patent Document 4) have been made. However, a transparent resin obtained by polymerizing a compound having an episulfide group is obtained by polymerizing a metal-containing compound such as Se in terms of mechanical properties in the case of a compound having a thietane group. Further improvement is desired in each of the obtained resins in terms of further improving safety. Recently, optical resins having various properties necessary for a plastic lens (transparency, thermal properties, mechanical properties, etc.) and a refractive index exceeding 1.7, for example, have a higher refractive index. Is being developed. Under such circumstances, a metal-containing thietane compound has been newly found, and an optical resin having a high refractive index exceeding a refractive index of 1.7 has been proposed (Patent Document 5).

  Such optical resins are required to have a high refractive index and excellent transparency, but in general, the resin may be colored yellow. For example, improvement of hue is a problem for optical resins having a high refractive index exceeding 1.7. On the other hand, a method of adding a bluing agent has been proposed for episulfide compounds, and a certain hue improvement effect has been obtained (Patent Document 6).

Japanese Patent Laid-Open No. 9-110979 JP 11-322930 A JP 2003-327583 A Japanese Patent Laid-Open No. 11-140046 International Publication No. 2005/095490 Pamphlet JP 2001-166101 A

  However, in general, it has been difficult to adjust and control the hue of an optical resin using a bluing agent, for reasons such as poor compatibility or compatibility between the bluing agent and the resin. For example, the interaction between the component in the optical resin and the bluing agent may change the hue, and it may be difficult to obtain the effect according to the hue of the bluing agent used.

  The present invention has various characteristics (transparency, thermal characteristics, mechanical characteristics, etc.) necessary for optical parts such as plastic lenses, and a very high refractive index exceeding a refractive index (ne) of 1.7. And a polymerizable composition that gives a resin having excellent transparency.

In order to solve the above-mentioned problems, the present inventors have made extensive studies on the previously proposed metal-containing thietane compound. As a result, the resin obtained by polymerizing the metal-containing thietane compound and the bluing agent is yellowed from the optical resin. It was found that a resin having excellent transparency and reduced yellowness can be obtained, and the present invention has been achieved.
That is, the present invention
[1] A polymerizable composition having one or more thietane groups and a metal atom in the molecule, and a compound represented by the following general formula (1) and a bluing agent:

(In the general formula (1), M represents a metal atom, X ₁ and X ₂ each independently represents a sulfur atom or an oxygen atom, R ₁ represents a divalent organic group, and m represents 0 or 1) When p represents an integer of 1 to n, n represents a valence of the metal atom M, Y represents each independently an inorganic or organic residue, and np is 2 or more, Y may be bonded to each other to form a ring containing a metal atom M.)
[2] The polymerizable composition as set forth in [1], further comprising a thiol compound;
[3] The polymerizable composition as set forth in [2], further comprising an epoxy compound and / or an episulfide compound;
[4] In the polymerizable composition according to [3], the thiol compound, the epoxy compound, and the compound represented by the general formula (1), the thiol compound, the epoxy compound, and the episulfide compound with respect to 100 parts by weight in total. A polymerizable composition, wherein the total of the episulfide compounds is 1 part by weight or more and 50 parts by weight or less;
[5] The polymerizable composition as set forth in [1], wherein the bluing agent is a dye;
[6] The polymerizable composition as described in [5], wherein the bluing agent is a dye containing one or more dyes selected from blue dyes and violet dyes;
[7] The polymerizable composition as set forth in [6], wherein the content of the bluing agent is in the range of 0.001 ppm to 500 ppm with respect to the total weight of the polymerizable compound contained in the polymerizable composition. A polymerizable composition;
[8] The polymerizable composition as set forth in [1], wherein the metal atom is a group 4, 8, 10, 11, 12, 13, 14, or 15 of the periodic table. Any of the polymerizable compositions;
[9] The polymerizable composition as set forth in [8], wherein the metal atom is any one of Group 4, Group 12, Group 13 and Group 14 of the long-period periodic table;
[10] The polymerizable composition as set forth in [9], wherein the metal atom is a Sn atom;
[11] The polymerizable composition as set forth in [1], wherein m = 0;
[12] The polymerizable composition as set forth in [11], wherein X ₁ is a sulfur atom;
[13] The polymerizable composition as set forth in [12], wherein n = p;
[14] The polymerizable composition as set forth in [13], wherein the metal atom is a Sn atom;
[15] The polymerizable composition as set forth in [14], further comprising a thiol compound;
[16] The polymerizable composition as set forth in [15], further comprising an epoxy compound and / or an episulfide compound;
[17] A method for producing a resin, comprising a step of cast polymerization of the polymerizable composition according to [1];
[18] A resin obtained by polymerizing the polymerizable composition according to [1];
[19] An optical component made of the resin according to [18]; and a lens made of the resin according to [20] [18].

  The resin obtained by polymerizing the polymerizable composition of the present invention is excellent in transparency and reduced in yellowness and has a high refractive index exceeding a refractive index (ne) of 1.7, such as a plastic lens. It is useful as a resin used for optical parts.

  Hereinafter, the present invention will be described in detail.

The present invention relates to a polymerizable composition containing a compound represented by the following general formula (1) and a bluing agent.
Hereinafter, although each component is demonstrated using a specific example, this invention is not limited to the following exemplary compounds. Moreover, in this invention, about each component, an exemplary compound may be used independently and may be used in multiple combination.

  First, general formula (1) will be described. The polymerizable composition of the present invention is a compound represented by the following general formula (1) as a compound represented by the following general formula (1), and a plurality of different compounds may be used in combination. There is no problem.

(In the general formula (1), M represents a metal atom, X ₁ and X ₂ each independently represent a sulfur atom or an oxygen atom, R ₁ represents a divalent organic group, and m represents 0 or 1) When p represents an integer of 1 to n, n represents a valence of the metal atom M, Y represents each independently an inorganic or organic residue, and np is 2 or more, Y may be bonded to each other to form a ring containing a metal atom M.)

First, M in the general formula (1) will be described. In the general formula (1), M represents a metal atom. M is a group 11 element of a long-period periodic table (hereinafter the same), such as Cu atom, Au atom, Ag atom;
Group 12 elements such as Zn atoms;
Group 13 elements such as Al atoms;
Group 4 elements such as Zr atoms and Ti atoms;
Group 14 elements such as Sn atom, Si atom, Ge atom, Pb atom;
Group 15 elements such as Sb atoms and Bi atoms; and Group 8 or 10 elements such as Fe atoms and Pt atoms.

M is preferably
Group 14 elements such as Sn atom, Si atom, Ge atom, Pb atom;
Group 4 elements such as Zr atoms and Ti atoms;
Group 13 elements such as Al atoms; or Group 12 elements such as Zn atoms, more preferably Group 14 elements such as Sn atoms, Si atoms and Ge atoms, or Group 4 elements such as Zr atoms and Ti atoms More specifically, it is a Sn atom.

Next, the group which contains thietanyl group and couple | bonds with M in the said General formula (1) is demonstrated. In the general formula (1), X ₁ and X ₂ each independently represent a sulfur atom or an oxygen atom. In view of the high refractive index which is a desired effect of the present invention, sulfur atoms are more preferable as X ₁ and X ₂ .

In the general formula (1), R ₁ represents a divalent organic group.
Examples of the divalent organic group include a chain or cyclic aliphatic group, an aromatic group, and an aromatic-aliphatic group, and preferably a chain aliphatic group having 1 to 20 carbon atoms and 3 carbon atoms. A cyclic aliphatic group having 20 or less or less, an aromatic group having 5 to 20 carbon atoms, and an aromatic-aliphatic group having 6 to 20 carbon atoms.

More specifically, R ₁ is such that the divalent organic group is a chain or cyclic aliphatic group, an aromatic group or an aromatic-aliphatic group,
Methylene group, ethylene group, 1,2-dichloroethylene group, trimethylene group, tetramethylene group, pentamethylene group, cyclopentylene group, hexamethylene group, cyclohexylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group A substituted or unsubstituted chain or cyclic aliphatic group having 1 to 20 carbon atoms, such as, undecamethylene group, dodecamethylene group, tridecamethylene group, tetradecamethylene group, pentadecamethylene group, etc .;
A substituted or unsubstituted aromatic group having 5 to 20 carbon atoms, such as a phenylene group, a chlorophenylene group, a naphthylene group, an indenylene group, an anthracenylene group, a fluorenylene group; or a —C ₆ H ₄ —CH ₂ — group, —CH ₂ -C ₆ H ₄ -CH ₂ - _{group, -CH 2 -C 6 H 3 (} Cl) -CH 2 - group, -C ₁₀ H ₆ -CH ₂ - group, -CH ₂ -C ₁₀ H ₆ -CH ₂ - _{group, -CH 2 CH 2 -C 6 H} 4 -CH 2 CH 2 - substituted or unsubstituted 6 to 20 aromatic carbons of such groups - is an aliphatic group.

R ₁ is more preferably a substituted or unsubstituted chain or cyclic fatty acid having 1 to 6 carbon atoms, such as a methylene group, an ethylene group, a 1,2-dichloroethylene group, a trimethylene group, a cyclopentylene group, and a cyclohexylene group. Group;
A substituted or unsubstituted aromatic group having 5 to 15 carbon atoms, such as a phenylene group, a chlorophenylene group, a naphthylene group, an indenylene group, an anthracenylene group, a fluorenylene group; or a —C ₆ H ₄ —CH ₂ — group, —CH ₂ -C ₆ H ₄ -CH ₂ - _{group, -CH 2 -C 6 H 3 (} Cl) -CH 2 - group, -C ₁₀ H ₆ -CH ₂ - group, -CH ₂ -C ₁₀ H ₆ -CH ₂ - _{group, -CH 2 CH 2 -C 6 H} 4 -CH 2 CH 2 - substituted or unsubstituted 15 following aromatic having 6 or more carbon atoms such as a group - is an aliphatic group.

  Such a divalent organic group may contain a hetero atom other than a carbon atom and a hydrogen atom in the group. Examples of such a hetero atom include an oxygen atom or a sulfur atom, but a sulfur atom is preferable in consideration of a desired effect of the present invention.

In the above general formula (1), m represents 0 or an integer of 1 or more.
Such m is preferably an integer of 0 or more and 4 or less, more preferably an integer of 0 or more and 2 or less, and still more preferably an integer 0 or 1. Even more preferably, m = 0 and X ₁ is a sulfur atom. At this time, the general formula (1) is represented by the following general formula (12).

(In the general formula (12), M, Y, p and n are the same as M, Y, p and n in the general formula (1), respectively.)

  In the general formula (12), preferably n = p, more preferably n = p and M is Sn.

Next,-(Y) _np group couple _| bonded with M in the said General formula (1) is _demonstrated .
In the general formula (1), n represents the valence of the metal atom M.

In the general formula (1), p represents an integer of 1 or more and n or less.
Such p is preferably n, n-1 or n-2, more preferably n or n-1.

In the general formula (1), each Y independently represents an inorganic or organic residue.
When the compound represented by the general formula (1) includes a plurality of Y, each of the plurality of Y independently represents an inorganic or organic residue. That is, the plurality of Y may be the same group or different groups. More specifically, each of the plurality of Y may be different from each other, a part of the plurality of Y may be a common group, or all of the plurality of Y may be the same group. Good.

  The inorganic or organic residue constituting Y is not particularly limited, and examples thereof include a hydrogen atom, a halogen atom, a hydroxyl group, a thiol group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, A substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted aryloxy group, and a substituted or unsubstituted arylthio group are shown.

  Among these, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkoxy (alkyloxy) group, a substituted or unsubstituted alkylthio group The substituted or unsubstituted aryloxy group and the substituted or unsubstituted arylthio group will be described below.

Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Specific examples of the substituted or unsubstituted alkyl group include a straight chain having 1 to 10 carbon atoms in total such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, and an n-hexyl group. An alkyl group;
iso-propyl group, isobutyl group, sec-butyl group, isopentyl group, sec-pentyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1-methylhexyl group, 2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 1-ethylpentyl group, 2-ethylpentyl group, 3-ethyl Pentyl group, 1-n-propylbutyl group, 1-iso-propylbutyl group, 1-iso-propyl-2-methylpropyl group, 1-methylheptyl group, 2-methylheptyl group, 3-methylheptyl group, 4 -Methylheptyl group, 5-methylheptyl group, 6-methylheptyl group, 1-ethylhexyl group, 2-ethylhexyl group 3-ethylhexyl group, 4-ethylhexyl group, 1-n-propylpentyl group, 2-n-propylpentyl group, 1-iso-propylpentyl group, 2-iso-propylpentyl group, 1-n-butylbutyl group, 1 -Iso-butylbutyl group, 1-sec-butylbutyl group, 1-tert-butylbutyl group, 2-tert-butylbutyl group, tert-butyl group, tert-pentyl group, 1,1-dimethylbutyl group, 1,2-dimethyl Butyl group, 1,3-dimethylbutyl group, 2,3-dimethylbutyl group, 1-ethyl-2-methylpropyl group, 1,1-dimethylpentyl group, 1,2-dimethylpentyl group, 1,3-dimethyl Pentyl group, 1,4-dimethylpentyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethyl Rupentyl group, 3,3-dimethylpentyl group, 3,4-dimethylpentyl group, 1-ethyl-1-methylbutyl group, 1-ethyl-2-methylbutyl group, 1-ethyl-3-methylbutyl group, 2-ethyl- 1-methylbutyl group, 2-ethyl-3-methylbutyl group, 1,1-dimethylhexyl group, 1,2-dimethylhexyl group, 1,3-dimethylhexyl group, 1,4-dimethylhexyl group, 1,5- Dimethylhexyl group, 2,2-dimethylhexyl group, 2,3-dimethylhexyl group, 2,4-dimethylhexyl group, 2,5-dimethylhexyl group, 3,3-dimethylhexyl group, 3,4-dimethylhexyl Group, 3,5-dimethylhexyl group, 4,4-dimethylhexyl group, 4,5-dimethylhexyl group, 1-ethyl-2-methylpentyl group, 1-ethyl -3-methylpentyl group, 1-ethyl-4-methylpentyl group, 2-ethyl-1-methylpentyl group, 2-ethyl-2-methylpentyl group, 2-ethyl-3-methylpentyl group, 2-ethyl -4-methylpentyl group, 3-ethyl-1-methylpentyl group, 3-ethyl-2-methylpentyl group, 3-ethyl-3-methylpentyl group, 3-ethyl-4-methylpentyl group, 1-n -Propyl-1-methylbutyl group, 1-n-propyl-2-methylbutyl group, 1-n-propyl-3-methylbutyl group, 1-iso-propyl-1-methylbutyl group, 1-iso-propyl-2-methylbutyl group Group, 1-iso-propyl-3-methylbutyl group, 1,1-diethylbutyl group, 1,2-diethylbutyl group, 1,1,2-trimethylpropyl group, 1,2,2 Trimethylpropyl group, 1,1,2-trimethylbutyl group, 1,1,3-trimethylbutyl group, 1,2,3-trimethylbutyl group, 1,2,2-trimethylbutyl group, 1,3,3- Trimethylbutyl, 2,3,3-trimethylbutyl, 1,1,2-trimethylpentyl, 1,1,3-trimethylpentyl, 1,1,4-trimethylpentyl, 1,2,2- Trimethylpentyl group, 1,2,3-trimethylpentyl group, 1,2,4-trimethylpentyl group, 1,3,4-trimethylpentyl group, 2,2,3-trimethylpentyl group, 2,2,4- Trimethylpentyl group, 2,3,4-trimethylpentyl group, 1,3,3-trimethylpentyl group, 2,3,3-trimethylpentyl group, 3,3,4-trimethylpentyl group, 1,4,4 -Trimethylpentyl group, 2,4,4-trimethylpentyl group, 3,4,4-trimethylpentyl group, 1-ethyl-1,2-dimethylbutyl group, 1-ethyl-1,3-dimethylbutyl group, 1 -Ethyl-2,3-dimethylbutyl group, 2-ethyl-1,1-dimethylbutyl group, 2-ethyl-1,2-dimethylbutyl group, 2-ethyl-1,3-dimethylbutyl group, 2-ethyl A branched alkyl group having 3 to 10 carbon atoms in total, such as -2,3-dimethylbutyl group; and cyclopentyl group, cyclohexyl group, methylcyclopentyl group, methoxycyclopentyl group, methoxycyclohexyl group, methylcyclohexyl group, 1,2-dimethyl Cyclohexyl group, 1,3-dimethylcyclohexyl group, 1,4-dimethylcyclohexyl group, ethylcyclohexyl group And a saturated cyclic alkyl group having 5 to 10 carbon atoms in total.

Specific examples of the substituted or unsubstituted aryl group include aromatic hydrocarbons having a total carbon number of 20 or less, such as a phenyl group, a naphthyl group, an anthranyl group, and a cyclopentadienyl group;
2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2-ethylphenyl group, propylphenyl group, butylphenyl group, hexylphenyl group, cyclohexylphenyl group, octylphenyl group, 2-methyl-1- Naphthyl group, 3-methyl-1-naphthyl group, 4-methyl-1-naphthyl group, 5-methyl-1-naphthyl group, 6-methyl-1-naphthyl group, 7-methyl-1-naphthyl group, 8- Methyl-1-naphthyl group, 1-methyl-2-naphthyl group, 3-methyl-2-naphthyl group, 4-methyl-2-naphthyl group, 5-methyl-2-naphthyl group, 6-methyl-2-naphthyl group Group, 7-methyl-2-naphthyl group, 8-methyl-2-naphthyl group, 2-ethyl-1-naphthyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 3,6-dimethylphenyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,4,5-trimethylphenyl group, 2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, etc. An alkyl-substituted aryl group having a total carbon number of 20 or less;
2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 2-ethoxyphenyl group, propoxyphenyl group, butoxyphenyl group, hexyloxyphenyl group, cyclohexyloxyphenyl group, octyloxyphenyl group, 2-methoxy -1-naphthyl group, 3-methoxy-1-naphthyl group, 4-methoxy-1-naphthyl group, 5-methoxy-1-naphthyl group, 6-methoxy-1-naphthyl group, 7-methoxy-1-naphthyl group 8-methoxy-1-naphthyl group, 1-methoxy-2-naphthyl group, 3-methoxy-2-naphthyl group, 4-methoxy-2-naphthyl group, 5-methoxy-2-naphthyl group, 6-methoxy- 2-naphthyl group, 7-methoxy-2-naphthyl group, 8-methoxy-2-naphthyl group, 2-ethoxy-1-naphthyl Mono alkoxyaryl group having 10 or less substituted or total carbon number alkyloxy group is substituted unsubstituted 20 or less carbon atoms such as a group;
2,3-dimethoxyphenyl group, 2,4-dimethoxyphenyl group, 2,5-dimethoxyphenyl group, 2,6-dimethoxyphenyl group, 3,4-dimethoxyphenyl group, 3,5-dimethoxyphenyl group, 3, 6-dimethoxyphenyl group, 4,5-dimethoxy-1-naphthyl group, 4,7-dimethoxy-1-naphthyl group, 4,8-dimethoxy-1-naphthyl group, 5,8-dimethoxy-1-naphthyl group, A dialkoxyaryl group having a total carbon number of 20 or less substituted by a substituted or unsubstituted alkyloxy group having a carbon number of 10 or less, such as a 5,8-dimethoxy-2-naphthyl group;
2,3,4-trimethoxyphenyl group, 2,3,5-trimethoxyphenyl group, 2,3,6-trimethoxyphenyl group, 2,4,5-trimethoxyphenyl group, 2,4,6- A trialkoxyaryl group having a total carbon number of 20 or less substituted by a substituted or unsubstituted alkyloxy group having a carbon number of 10 or less, such as a trimethoxyphenyl group or a 3,4,5-trimethoxyphenyl group; and a chlorophenyl group or a dichlorophenyl group Halogen such as trichlorophenyl group, bromophenyl group, dibromophenyl group, iodophenyl group, fluorophenyl group, chloronaphthyl group, bromonaphthyl group, difluorophenyl group, trifluorophenyl group, tetrafluorophenyl group, pentafluorophenyl group An aryl group having a total of 20 or less carbon atoms substituted by an atom is exemplified.

  Specific examples of the substituted or unsubstituted aralkyl group include aralkyl groups having a total carbon number of 12 or less such as a benzyl group, a phenethyl group, a phenylpropyl group, and a naphthylethyl group, and specific examples of a substituted or unsubstituted aryl group. And methyl group, ethyl group, and propyl group having an aryl group in the side chain.

Specific examples of the substituted or unsubstituted alkyloxy group include methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, iso-butoxy group, tert-butoxy group, n-pentyloxy group, iso-pentyloxy group, n-hexyloxy group, iso-hexyloxy group, 2-ethylhexyloxy group, 3,5,5-trimethylhexyloxy group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group A linear or branched alkoxy group having 1 to 10 carbon atoms in total, such as a group;
A cycloalkoxy group having 5 to 10 carbon atoms in total, such as a cyclopentyloxy group and a cyclohexyloxy group;
Methoxymethoxy group, ethoxymethoxy group, ethoxyethoxy group, n-propoxymethoxy group, iso-propoxymethoxy group, n-propoxyethoxy group, iso-propoxyethoxy group, n-butoxyethoxy group, iso-butoxyethoxy group, tert- Alkoxyalkoxy having 2 to 10 carbon atoms in total such as butoxyethoxy group, n-pentyloxyethoxy group, iso-pentyloxyethoxy group, n-hexyloxyethoxy group, iso-hexyloxyethoxy group, n-heptyloxyethoxy group Groups; and aralkyloxy groups such as benzyloxy groups.

Specific examples of the substituted or unsubstituted alkylthio group include methylthio group, ethylthio group, n-propylthio group, iso-propylthio group, n-butylthio group, iso-butylthio group, sec-butylthio group, t-butylthio group, n- Pentylthio group, iso-pentylthio group, n-hexylthio group, iso-hexylthio group, 2-ethylhexylthio group, 3,5,5-trimethylhexylthio group, n-heptylthio group, n-octylthio group, n-nonylthio group, etc. A linear or branched alkylthio group having 1 to 10 carbon atoms in total;
A cycloalkylthio group having 5 to 10 carbon atoms in total, such as a cyclopentylthio group and a cyclohexylthio group;
Methoxyethylthio group, ethoxyethylthio group, n-propoxyethylthio group, iso-propoxyethylthio group, n-butoxyethylthio group, iso-butoxyethylthio group, tert-butoxyethylthio group, n-pentyloxyethyl An alkoxyalkylthio group having 2 to 10 carbon atoms in total such as a thio group, an iso-pentyloxyethylthio group, an n-hexyloxyethylthio group, an iso-hexyloxyethylthio group, and an n-heptyloxyethylthio group;
Aralkylthio groups such as benzylthio group; and methylthioethylthio group, ethylthioethylthio group, n-propylthioethylthio group, iso-propylthioethylthio group, n-butylthioethylthio group, iso-butylthioethylthio group Group, tert-butylthioethylthio group, n-pentylthioethylthio group, iso-pentylthioethylthio group, n-hexylthioethylthio group, iso-hexylthioethylthio group, n-heptylthioethylthio group, etc. And an alkylthioalkylthio group having 2 to 10 carbon atoms in total.

Specific examples of the substituted or unsubstituted aryloxy group include a phenyloxy group, a naphthyloxy group, an anthranyloxy group, a 2-methylphenyloxy group, a 3-methylphenyloxy group, a 4-methylphenyloxy group, and 2-ethyl. Phenyloxy group, propylphenyloxy group, butylphenyloxy group, hexylphenyloxy group, cyclohexylphenyloxy group, octylphenyloxy group, 2-methyl-1-naphthyloxy group, 3-methyl-1-naphthyloxy group, 4 -Methyl-1-naphthyloxy group, 5-methyl-1-naphthyloxy group, 6-methyl-1-naphthyloxy group, 7-methyl-1-naphthyloxy group, 8-methyl-1-naphthyloxy group, 1 -Methyl-2-naphthyloxy group, 3-methyl-2-naphthyloxy group, 4-methyl Ru-2-naphthyloxy group, 5-methyl-2-naphthyloxy group, 6-methyl-2-naphthyloxy group, 7-methyl-2-naphthyloxy group, 8-methyl-2-naphthyloxy group, 2- Ethyl-1-naphthyloxy group, 2,3-dimethylphenyloxy group, 2,4-dimethylphenyloxy group, 2,5-dimethylphenyloxy group, 2,6-dimethylphenyloxy group, 3,4-dimethylphenyl Oxy group, 3,5-dimethylphenyloxy group, 3,6-dimethylphenyloxy group, 2,3,4-trimethylphenyloxy group, 2,3,5-trimethylphenyloxy group, 2,3,6-trimethyl Phenyloxy group, 2,4,5-trimethylphenyloxy group, 2,4,6-trimethylphenyloxy group, 3,4,5-trimethylphenyl Alkoxy unsubstituted or alkyl-substituted aryloxy group having a total carbon number of 20 or less, such groups;
2-methoxyphenyloxy group, 3-methoxyphenyloxy group, 4-methoxyphenyloxy group, 2-ethoxyphenyloxy group, propoxyphenyloxy group, butoxyphenyloxy group, hexyloxyphenyloxy group, cyclohexyloxyphenyloxy group, Octyloxyphenyloxy group, 2-methoxy-1-naphthyloxy group, 3-methoxy-1-naphthyloxy group, 4-methoxy-1-naphthyloxy group, 5-methoxy-1-naphthyloxy group, 6-methoxy- 1-naphthyloxy group, 7-methoxy-1-naphthyloxy group, 8-methoxy-1-naphthyloxy group, 1-methoxy-2-naphthyloxy group, 3-methoxy-2-naphthyloxy group, 4-methoxy- 2-naphthyloxy group, 5-methoxy-2-naphthyloxy group A substituent having 10 or less carbon atoms such as a group, 6-methoxy-2-naphthyloxy group, 7-methoxy-2-naphthyloxy group, 8-methoxy-2-naphthyloxy group, 2-ethoxy-1-naphthyloxy group, or the like; A monoalkoxyaryloxy group having a total carbon number of 20 or less substituted by an unsubstituted alkyloxy group;
2,3-dimethoxyphenyloxy group, 2,4-dimethoxyphenyloxy group, 2,5-dimethoxyphenyloxy group, 2,6-dimethoxyphenyloxy group, 3,4-dimethoxyphenyloxy group, 3,5-dimethoxy Phenyloxy group, 3,6-dimethoxyphenyloxy group, 4,5-dimethoxy-1-naphthyloxy group, 4,7-dimethoxy-1-naphthyloxy group, 4,8-dimethoxy-1-naphthyloxy group, 5 , 8-dimethoxy-1-naphthyloxy group, 5,8-dimethoxy-2-naphthyloxy group and the like substituted or unsubstituted alkyloxy group substituted with a total of 20 or less dialkoxyaryloxy Group;
2,3,4-trimethoxyphenyloxy group, 2,3,5-trimethoxyphenyloxy group, 2,3,6-trimethoxyphenyloxy group, 2,4,5-trimethoxyphenyloxy group, 2, A trialkoxyaryloxy group having a total carbon number of 20 or less substituted by a substituted or unsubstituted alkyloxy group having a carbon number of 10 or less, such as a 4,6-trimethoxyphenyloxy group or a 3,4,5-trimethoxyphenyloxy group Chlorophenyloxy group, dichlorophenyloxy group, trichlorophenyloxy group, bromophenyloxy group, dibromophenyloxy group, iodophenyloxy group, fluorophenyloxy group, chloronaphthyloxy group, bromonaphthyloxy group, difluorophenyloxy group, Trifluorophenyloxy group, tetrafluoro Phenyloxy group, a halogen atom such as a pentafluorophenyl group and the aryloxy group having not more than a total carbon number of 20 has been substituted.

Specific examples of the substituted or unsubstituted arylthio group include a phenylthio group, a naphthylthio group, an anthranylthio group, a 2-methylphenylthio group, a 3-methylphenylthio group, a 4-methylphenylthio group, and a 2-ethylphenylthio group. Propylphenylthio group, butylphenylthio group, hexylphenylthio group, cyclohexylphenylthio group, octylphenylthio group, 2-methyl-1-naphthylthio group, 3-methyl-1-naphthylthio group, 4-methyl-1- Naphthylthio group, 5-methyl-1-naphthylthio group, 6-methyl-1-naphthylthio group, 7-methyl-1-naphthylthio group, 8-methyl-1-naphthylthio group, 1-methyl-2-naphthylthio group, 3- Methyl-2-naphthylthio group, 4-methyl-2-naphthylthio group, 5-methyl-2-na Tilthio group, 6-methyl-2-naphthylthio group, 7-methyl-2-naphthylthio group, 8-methyl-2-naphthylthio group, 2-ethyl-1-naphthylthio group, 2,3-dimethylphenylthio group, 2, 4-dimethylphenylthio group, 2,5-dimethylphenylthio group, 2,6-dimethylphenylthio group, 3,4-dimethylphenylthio group, 3,5-dimethylphenylthio group, 3,6-dimethylphenylthio group Group, 2,3,4-trimethylphenylthio group, 2,3,5-trimethylphenylthio group, 2,3,6-trimethylphenylthio group, 2,4,5-trimethylphenylthio group, 2,4, An unsubstituted or alkyl-substituted arylthio group having a total carbon number of 20 or less, such as a 6-trimethylphenylthio group or a 3,4,5-trimethylphenylthio group;
2-methoxyphenylthio group, 3-methoxyphenylthio group, 4-methoxyphenylthio group, 2-ethoxyphenylthio group, propoxyphenylthio group, butoxyphenylthio group, hexyloxyphenylthio group, cyclohexyloxyphenylthio group, Octyloxyphenylthio group, 2-methoxy-1-naphthylthio group, 3-methoxy-1-naphthylthio group, 4-methoxy-1-naphthylthio group, 5-methoxy-1-naphthylthio group, 6-methoxy-1-naphthylthio group 7-methoxy-1-naphthylthio group, 8-methoxy-1-naphthylthio group, 1-methoxy-2-naphthylthio group, 3-methoxy-2-naphthylthio group, 4-methoxy-2-naphthylthio group, 5-methoxy- 2-naphthylthio group, 6-methoxy-2-naphthylthio group, Mono having no more than 20 carbon atoms substituted by a substituted or unsubstituted alkyloxy group having not more than 10 carbon atoms such as -methoxy-2-naphthylthio group, 8-methoxy-2-naphthylthio group, 2-ethoxy-1-naphthylthio group, etc. An alkoxyarylthio group;
2,3-dimethoxyphenylthio group, 2,4-dimethoxyphenylthio group, 2,5-dimethoxyphenylthio group, 2,6-dimethoxyphenylthio group, 3,4-dimethoxyphenylthio group, 3,5-dimethoxy Phenylthio group, 3,6-dimethoxyphenylthio group, 4,5-dimethoxy-1-naphthylthio group, 4,7-dimethoxy-1-naphthylthio group, 4,8-dimethoxy-1-naphthylthio group, 5,8- A dialkoxyarylthio group having a total carbon number of 20 or less substituted by a substituted or unsubstituted alkyloxy group having a carbon number of 10 or less, such as a dimethoxy-1-naphthylthio group or a 5,8-dimethoxy-2-naphthylthio group;
2,3,4-trimethoxyphenylthio group, 2,3,5-trimethoxyphenylthio group, 2,3,6-trimethoxyphenylthio group, 2,4,5-trimethoxyphenylthio group, 2, A trialkoxyarylthio group having a total carbon number of 20 or less substituted by a substituted or unsubstituted alkyloxy group having a carbon number of 10 or less, such as a 4,6-trimethoxyphenylthio group or a 3,4,5-trimethoxyphenylthio group. Chlorophenylthio group, dichlorophenylthio group, trichlorophenylthio group, bromophenylthio group, dibromophenylthio group, iodophenylthio group, fluorophenylthio group, chloronaphthylthio group, bromonaphthylthio group, difluorophenylthio group, Trifluorophenylthio group, tetrafluorophenylthio group, pentafluorophene Total of 20 or less arylthio group such as carbon halogen atom-substituted, such as thio group. Y is not limited to these.

Preferred examples of such Y are shown below.
A preferred example is a hydrogen atom.

Among preferred examples of Y, examples of the halogen atom include a chlorine atom, a bromine atom, and an iodine atom.
As a substituted or unsubstituted alkyl group, a straight chain alkyl group having 1 to 6 carbon atoms in total, such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, and an n-hexyl group;
iso-propyl group, isobutyl group, sec-butyl group, isopentyl group, sec-pentyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1-ethylbutyl group, 2-ethylbutyl group, tert-butyl group, tert-pentyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,3-dimethylbutyl group, etc. A branched alkyl group having 3 to 6 carbon atoms; and a saturated cyclic alkyl group having 5 or 6 carbon atoms in total, such as a cyclopentyl group and a cyclohexyl group.

An aromatic hydrocarbon having a total carbon number of 12 or less, such as a phenyl group, a naphthyl group, a cyclopentadienyl group, as a substituted or unsubstituted aryl group;
2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2-ethylphenyl group, propylphenyl group, butylphenyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2, 5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 3,6-dimethylphenyl group, 2,3,4-trimethylphenyl group, 2, 3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,4,5-trimethylphenyl group, 2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, etc. An alkyl-substituted aryl group having 12 or less carbon atoms;
Substituted or unsubstituted alkyloxy groups having 6 or less carbon atoms such as 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 2-ethoxyphenyl group, propoxyphenyl group, butoxyphenyl group, etc. A monoalkoxyaryl group having a total carbon number of 12 or less;
2,3-dimethoxyphenyl group, 2,4-dimethoxyphenyl group, 2,5-dimethoxyphenyl group, 2,6-dimethoxyphenyl group, 3,4-dimethoxyphenyl group, 3,5-dimethoxyphenyl group, 3, A dialkoxyaryl group having a total carbon number of 12 or less substituted by a substituted or unsubstituted alkyloxy group having a carbon number of 6 or less such as 6-dimethoxyphenyl group; and a chlorophenyl group, a dichlorophenyl group, a trichlorophenyl group, a bromophenyl group, a dibromo Total carbon number of 12 or less substituted with halogen atoms such as phenyl group, iodophenyl group, fluorophenyl group, chloronaphthyl group, bromonaphthyl group, difluorophenyl group, trifluorophenyl group, tetrafluorophenyl group, pentafluorophenyl group An aryl group is mentioned.

  Examples of the substituted or unsubstituted aralkyl group include aralkyl groups having a total carbon number of 12 or less, such as a benzyl group, a phenethyl group, and a phenylpropyl group.

As substituted or unsubstituted alkyloxy groups, methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, iso-butoxy group, tert-butoxy group, n-pentyloxy group, iso-pentyl A linear or branched alkoxy group having 1 to 6 carbon atoms in total, such as an oxy group, an n-hexyloxy group, an iso-hexyloxy group;
A cycloalkoxy group having 5 or 6 carbon atoms in total such as cyclopentyloxy group and cyclohexyloxy group; and methoxymethoxy group, ethoxymethoxy group, ethoxyethoxy group, n-propoxymethoxy group, iso-propoxymethoxy group, n-propoxyethoxy group , An alkoxyalkoxy group having 2 to 6 carbon atoms in total such as iso-propoxyethoxy group, n-butoxyethoxy group, iso-butoxyethoxy group, tert-butoxyethoxy group, and the like.

As the substituted or unsubstituted alkylthio group, methylthio group, ethylthio group, n-propylthio group, iso-propylthio group, n-butylthio group, iso-butylthio group, sec-butylthio group, t-butylthio group, n-pentylthio group, a linear or branched alkylthio group having 1 to 6 carbon atoms in total, such as an iso-pentylthio group, an n-hexylthio group, an iso-hexylthio group;
A cycloalkylthio group having 5 or 6 carbon atoms in total such as a cyclopentylthio group and a cyclohexylthio group;
Total carbon number 2 such as methoxyethylthio group, ethoxyethylthio group, n-propoxyethylthio group, iso-propoxyethylthio group, n-butoxyethylthio group, iso-butoxyethylthio group, tert-butoxyethylthio group 6 or less alkoxyalkylthio group; and methylthioethylthio group, ethylthioethylthio group, n-propylthioethylthio group, iso-propylthioethylthio group, n-butylthioethylthio group, iso-butylthioethylthio group And an alkylthioalkylthio group having 2 to 6 carbon atoms in total, such as a tert-butylthioethylthio group.

As substituted or unsubstituted aryloxy group, phenyloxy group, naphthyloxy group, 2-methylphenyloxy group, 3-methylphenyloxy group, 4-methylphenyloxy group, 2-ethylphenyloxy group, propylphenyloxy group Butylphenyloxy group, hexylphenyloxy group, cyclohexylphenyloxy group, 2,4-dimethylphenyloxy group, 2,5-dimethylphenyloxy group, 2,6-dimethylphenyloxy group, 3,4-dimethylphenyloxy group Group, 3,5-dimethylphenyloxy group, 3,6-dimethylphenyloxy group, 2,3,4-trimethylphenyloxy group, 2,3,5-trimethylphenyloxy group, 2,3,6-trimethylphenyl Oxy group, 2,4,5-trimethylphenyloxy group, 2, , 6-trimethylphenyl group, 3,4,5-trimethylphenyl unsubstituted or alkyl-substituted aryloxy group having a total carbon number of 12 or less, such as oxy group;
2-methoxyphenyloxy group, 3-methoxyphenyloxy group, 4-methoxyphenyloxy group, 2-ethoxyphenyloxy group, propoxyphenyloxy group, butoxyphenyloxy group, hexyloxyphenyloxy group, cyclohexyloxyphenyloxy group, etc. A monoalkoxyaryloxy group having a total carbon number of 12 or less substituted by a substituted or unsubstituted alkyloxy group having a carbon number of 6 or less;
2,3-dimethoxyphenyloxy group, 2,4-dimethoxyphenyloxy group, 2,5-dimethoxyphenyloxy group, 2,6-dimethoxyphenyloxy group, 3,4-dimethoxyphenyloxy group, 3,5-dimethoxy A dialkoxyaryloxy group having a total carbon number of 12 or less substituted by a substituted or unsubstituted alkyloxy group having a carbon number of 6 or less, such as a phenyloxy group or a 3,6-dimethoxyphenyloxy group; and a chlorophenyloxy group or a dichlorophenyloxy group , Trichlorophenyloxy group, bromophenyloxy group, dibromophenyloxy group, iodophenyloxy group, fluorophenyloxy group, chloronaphthyloxy group, bromonaphthyloxy group, difluorophenyloxy group, trifluorophenyloxy group, tetrafluorophenyl Niruokishi group, a halogen atom such as a pentafluorophenyl group and the aryloxy group having not more than a total carbon number of 12 has been substituted.

As a substituted or unsubstituted arylthio group, phenylthio group, naphthylthio group, 2-methylphenylthio group, 3-methylphenylthio group, 4-methylphenylthio group, 2-ethylphenylthio group, propylphenylthio group, butylphenyl Thio group, hexylphenylthio group, cyclohexylphenylthio group, 2,4-dimethylphenylthio group, 2,5-dimethylphenylthio group, 2,6-dimethylphenylthio group, 3,4-dimethylphenylthio group, 3 , 5-dimethylphenylthio group, 3,6-dimethylphenylthio group, 2,3,4-trimethylphenylthio group, 2,3,5-trimethylphenylthio group, 2,3,6-trimethylphenylthio group, 2,4,5-trimethylphenylthio group, 2,4,6-trimethylphenylthio group, 3,4, - unsubstituted or alkyl-substituted arylthio group having a total carbon number of 12 or less, such as trimethylphenyl thio group;
2-methoxyphenylthio group, 3-methoxyphenylthio group, 4-methoxyphenylthio group, 2-ethoxyphenylthio group, propoxyphenylthio group, butoxyphenylthio group, hexyloxyphenylthio group, cyclohexyloxyphenylthio group, etc. A monoalkoxyarylthio group having a total carbon number of 12 or less substituted by a substituted or unsubstituted alkyloxy group having a carbon number of 6 or less;
2,3-dimethoxyphenylthio group, 2,4-dimethoxyphenylthio group, 2,5-dimethoxyphenylthio group, 2,6-dimethoxyphenylthio group, 3,4-dimethoxyphenylthio group, 3,5-dimethoxy Phenylthio group, 3,6-dimethoxyphenylthio group, 4,5-dimethoxy-1-naphthylthio group, 4,7-dimethoxy-1-naphthylthio group, 4,8-dimethoxy-1-naphthylthio group, 5,8- A dialkoxyarylthio group having a total carbon number of 12 or less substituted by a substituted or unsubstituted alkyloxy group having a carbon number of 6 or less, such as a dimethoxy-1-naphthylthio group or a 5,8-dimethoxy-2-naphthylthio group;
Chlorophenylthio group, dichlorophenylthio group, trichlorophenylthio group, bromophenylthio group, dibromophenylthio group, iodophenylthio group, fluorophenylthio group, chloronaphthylthio group, bromonaphthylthio group, difluorophenylthio group, trifluoro Examples thereof include arylthio groups having a total carbon number of 12 or less substituted with halogen atoms such as a phenylthio group, a tetrafluorophenylthio group, and a pentafluorophenylthio group.

More preferred examples of Y are shown below.
More preferred examples of Y include a hydrogen atom.
Moreover, a chlorine atom and a bromine atom are mentioned as a halogen atom.

  Examples of the substituted or unsubstituted alkyl group include linear or branched alkyl groups having 1 to 3 carbon atoms in total, such as a methyl group, an ethyl group, and an iso-propyl group.

An aromatic hydrocarbon having a total carbon number of 12 or less, such as a phenyl group, a naphthyl group, a cyclopentadienyl group, as a substituted or unsubstituted aryl group;
2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2-ethylphenyl group, propylphenyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl An alkyl-substituted aryl group having a total carbon number of 9 or less, such as a group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 3,6-dimethylphenyl group;
Total carbon number of 9 or less substituted by a substituted or unsubstituted alkyloxy group having 3 or less carbon atoms such as 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 2-ethoxyphenyl group, propoxyphenyl group, etc. And aryl groups having a total carbon number of 12 or less substituted with halogen atoms such as chlorophenyl group, dichlorophenyl group, trichlorophenyl group, bromophenyl group, dibromophenyl group, chloronaphthyl group, and bromonaphthyl group. .

  Examples of the substituted or unsubstituted aralkyl group include aralkyl groups having a total carbon number of 9 or less, such as a benzyl group, a phenethyl group, and a phenylpropyl group.

As a substituted or unsubstituted alkyloxy group, a linear or branched alkoxy group having 1 to 3 carbon atoms in total such as a methoxy group, an ethoxy group, and an iso-propoxy group; and a total carbon such as a cyclopentyloxy group and a cyclohexyloxy group The cycloalkoxy group of number 5 or 6 is mentioned.

As a substituted or unsubstituted alkylthio group, a linear or branched alkylthio group having 1 to 3 carbon atoms in total such as a methylthio group, an ethylthio group, an n-propylthio group, an iso-propylthio group;
A cycloalkylthio group having 5 or 6 carbon atoms in total such as a cyclopentylthio group and a cyclohexylthio group; and a methylthioethylthio group, an ethylthioethylthio group, an n-propylthioethylthio group, an iso-propylthioethylthio group, an n- Examples thereof include alkylthioalkylthio groups having 2 to 6 carbon atoms in total, such as a butylthioethylthio group, an iso-butylthioethylthio group, and a tert-butylthioethylthio group.

As substituted or unsubstituted aryloxy group, phenyloxy group, naphthyloxy group, 2-methylphenyloxy group, 3-methylphenyloxy group, 4-methylphenyloxy group, 2-ethylphenyloxy group, propylphenyloxy group 2,4-dimethylphenyloxy group, 2,5-dimethylphenyloxy group, 2,6-dimethylphenyloxy group, 3,4-dimethylphenyloxy group, 3,5-dimethylphenyloxy group, 3,6- An unsubstituted or alkyl-substituted aryloxy group having a total carbon number of 9 or less, such as a dimethylphenyloxy group;
Substituted or unsubstituted alkyloxy groups having 3 or less carbon atoms such as 2-methoxyphenyloxy group, 3-methoxyphenyloxy group, 4-methoxyphenyloxy group, 2-ethoxyphenyloxy group, propoxyphenyloxy group, etc. A monoalkoxyaryloxy group having a total carbon number of 9 or less; and halogen atoms such as chlorophenyloxy group, dichlorophenyloxy group, trichlorophenyloxy group, bromophenyloxy group, dibromophenyloxy group, chloronaphthyloxy group, bromonaphthyloxy group Examples include substituted aryloxy groups having 12 or less carbon atoms.

As a substituted or unsubstituted arylthio group, phenylthio group, 2-methylphenylthio group, 3-methylphenylthio group, 4-methylphenylthio group, 2-ethylphenylthio group, propylphenylthio group, 2,4-dimethyl Phenylthio group, 2,5-dimethylphenylthio group, 2,6-dimethylphenylthio group, 3,4-dimethylphenylthio group, 3,5-dimethylphenylthio group, 3,6-dimethylphenylthio group, etc. An unsubstituted or alkyl-substituted arylthio group having a total carbon number of 9 or less;
Substituted or unsubstituted alkyloxy groups having 3 or less carbon atoms such as 2-methoxyphenylthio group, 3-methoxyphenylthio group, 4-methoxyphenylthio group, 2-ethoxyphenylthio group, propoxyphenylthio group A monoalkoxyarylthio group having a total carbon number of 9 or less; and halogen atoms such as a chlorophenylthio group, a dichlorophenylthio group, a trichlorophenylthio group, a bromophenylthio group, a dibromophenylthio group, a chloronaphthylthio group, and a bromonaphthylthio group A substituted arylthio group having a total carbon number of 12 or less can be mentioned.

  Moreover, when np is an integer greater than or equal to 2, Y may couple | bond together and may become a cyclic structure through the metal atom M. That is, a plurality of Y may be bonded to form a ring containing the metal atom M.

  Although the compound represented by the said General formula (1) is specifically illustrated by the following Table 1-Table 17, it is not limited to these. Tables 1 to 17 are tables showing specific examples of the compound represented by the general formula (1). In Tables 1 to 17, “CMPD. No.” means Compound No. That is.

In Tables 1 to 17, Y ₁ , Y ₂ , and Y ₃ represent Y when the total number of Y bonded to M is 3 or less, that is, the value of np is 3 or less. Specifically, when n−p = 1, Y is only Y ₁ . When n−p = 2, the compound contains Y ₁ and Y ₂ as Y, and these may be the same group or different groups. When np = 3, the compound contains Y ₁ , Y ₂ and Y ₃ as Y, and these may be the same group or different groups.
In the table, when np is 2, in a compound in which one group is described from Y ₁ to Y ₂ , two Ys are bonded to each other to form a ring containing a metal atom M. .

Among the compounds shown in Tables 1 to 17, specifically, in the general formula (1), a compound with m = 0 is used.
More specifically, a compound in which m = 0 and X ₁ is a sulfur atom is used. As such a compound, for example, among the compounds shown in Tables 1 to 17, CMPD. No. 1-1, 1-35, 1-37, 1-39, 1-41, 1-43, 1-45, 1-47, 1-49, 1-41, 1-53, 1-55, 1- 57, 1-59, 1-61, 1-63, 1-65, 1-67, 1-69, 1-71, 1-73, 1-75, 1-141, 1-175, 1-177, 1-179, 1-181, 1-183, 1-185, 1-187, 1-189, 1-191, 1-191, 1-193, 1-227, 1-229, 1-231, 1-233, 1- 235, 1-237, 1-239, 1-241, 1-243, 1-245, 1-247, 1-249, 1-267, 1-269, 1-287, 1-289, 1-291, 1-293, 1-295, 1-297, and 1-299 are listed.

In the general formula (1), as an example of a preferred, those wherein n = p and the like, more preferably, n = p, m = 0 , X 1 is a sulfur atom. As such a compound, for example, among the compounds shown in Tables 1 to 17, CMPD. No. 1-1, 1-141, 1-193, 1-245, 1-247, 1-267, 1-287, 1-289. Of these, it is more preferable that the metal atom M is any one element of Group 4, 12, 13, and 14 of the long periodic table, and the metal atom M is a Sn atom. Those are even more preferred.

  In addition, in the general formula (1), when np is 2 or more, that is, as an example in which the compound represented by the general formula (1) is a compound containing two or more Y in the molecule, The compound shown to a following formula is mentioned. In the following compounds, all three Ys are different groups.

Next, the manufacturing method of the compound represented by the said General formula (1) is demonstrated.
The compound represented by the general formula (1) is typically a hydroxy having a halide of a metal atom M represented by the following general formula (2) and a thietane group represented by the following general formula (3). Produced by reaction with compounds or thiol compounds.

(In the general formula (2), M, n, p and Y are the same as M, n, p and Y in the general formula (1), respectively, and Z represents a halogen atom.)

(In the general formula (3), X ₁ , X ₂ , R ₁ and m are the same as X ₁ , X ₂ , R ₁ and m in the general formula (1), respectively.)

The compound represented by the general formula (2) is available as an industrial raw material or a research reagent.
Further, the compound represented by the general formula (3) is a known compound, and is produced, for example, according to the method described in Patent Document 3 (Japanese Patent Application Laid-Open No. 2003-327583).

  The reaction between the halide of the metal atom M represented by the general formula (2) and the hydroxy compound or thiol compound having a thietane group represented by the general formula (3) may be performed without a solvent, or The reaction may be performed in the presence of a solvent inert to the reaction.

Such a solvent is not particularly limited as long as it is inert to the reaction, and is a hydrocarbon solvent such as petroleum ether, hexane, benzene, toluene, xylene, mesitylene;
Ether solvents such as diethyl ether, tetrahydrofuran, diethylene glycol dimethyl ether;
Ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone;
Ester solvents such as ethyl acetate, butyl acetate, amyl acetate;
Chlorine-containing solvents such as methylene chloride, chloroform, chlorobenzene, dichlorobenzene;
Aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylimidazolidinone, dimethyl sulfoxide;
Sulfur-containing solvents such as tetrahydrothiophene, thiophene, sulfolane, trimethylene sulfide, diethyl sulfide, di-n-propyl sulfide, di-t-butyl sulfide, 3-mercaptothietane, bis (2-mercaptoethyl) sulfide; and Examples include water.

  The reaction temperature between the compounds represented by the general formulas (2) and (3) is not particularly limited, but is usually in the range of −78 ° C. or higher and 200 ° C. or lower, preferably −78 ° C. or higher. It is 100 degrees C or less.

  The reaction time is influenced by the reaction temperature, but is usually from several minutes to 100 hours.

  The amount of the compound represented by the general formula (2) and the compound represented by the general formula (3) used in the reaction between the compound represented by the general formula (2) and (3) is particularly limited. However, the amount of the compound represented by the general formula (3) used is generally 0. 1 mol with respect to 1 mol of the halogen atom contained in the compound represented by the general formula (2). It is 01 mol or more and 100 mol or less. Preferably, it is 0.1 mol or more and 50 mol or less, More preferably, it is 0.5 mol or more and 20 mol or less.

In carrying out the reaction between the compounds represented by the general formulas (2) and (3), it is preferable to use a basic compound as a scavenger for the generated hydrogen halide in order to carry out the reaction efficiently.
Examples of such basic compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, sodium bicarbonate, potassium bicarbonate, lithium bicarbonate, magnesium hydroxide, and calcium hydroxide. Illustrative are inorganic bases; and organic bases such as pyridine, triethylamine, dimethylaniline, diethylaniline, 1,8-diazabicyclo [5,4,0] -7-undecene.

Next, the bluing agent will be described.
The bluing agent has an absorption band in the wavelength range from orange to yellow in the visible light region, and has a function of adjusting the hue of the resin. More specifically, the bluing agent contains a substance exhibiting a blue to purple color.

  The bluing agent used in the polymerizable composition of the present invention is not particularly limited, and specific examples include dyes, fluorescent whitening agents, fluorescent pigments, and inorganic pigments. Among those that can be used, it is appropriately selected according to the physical properties required for the lens, the resin hue, and the like. Of these, dyes are preferred from the viewpoint of solubility in the polymerizable composition and the transparency of the resulting resin.

  The amount of blueing agent used varies depending on the type of monomer, the presence or absence of various additives, the type and amount of additives used, the polymerization method, and the polymerization conditions. Used at a ratio of 0.001 ppm to 500 ppm, preferably 0.005 ppm to 100 ppm, more preferably 0.01 ppm to 10 ppm, based on the total weight of the polymerizable compound contained in the product. The If the amount of the bluing agent added is too large, the entire lens may become too blue, which may not be preferable. If the amount added is too small, the hue improving effect may not be sufficiently exhibited, which may be undesirable.

  The method for adding these bluing agents is not particularly limited, and it is desirable to add them to the monomer system in advance. Various methods, such as a method of preparing a master solution containing an inching agent and diluting the master solution with a monomer using the master solution or another additive, can be employed.

  The bluing agent used in the present invention is preferably a dye containing one or two or more dyes selected from blue dyes and violet dyes, but in some cases, other color dyes may be mixed. May be used. For example, in addition to blue and violet dyes, gray, brown, red and orange dyes can also be used. Specific examples of such a combination of bluing agents include a combination of a blue dye and a red dye, and a combination of a violet dye and a red dye.

  From the viewpoint of the absorption wavelength, a dye having a maximum absorption wavelength of 520 nm to 600 nm is preferable, and a dye having a maximum absorption wavelength of 540 nm to 580 nm is more preferable.

  Specific examples of dyes include “PS Blue RR”, “PS Violet RC”, “PET Blue 2000”, “PS Brilliant Red HEY”, “MLP RED V-1” (each trade name of Dystar Japan) ) And the like.

  As the optical brightener, those having good compatibility with the resin are preferable. For example, “UVITEX (registered trademark) OB”, “UVITEX OB-P” (trade name, manufactured by Ciba-Geigy Japan), “MIKEPHOR YO” , “MIKEPHOR ETN conc.”, “MIKEPHOR ETR conc.”, “MIKEPHOREB conc.” (Trade name, manufactured by Miike Dye), “KAYCALL E”, “KAYCALL C”, “KAYCALL PAN” (trade name, Nippon Soda) ), "WHITEX (registered trademark) ERN conc." (Trade name, manufactured by Sumitomo Chemical Co., Ltd.), "MIKAWHITE (registered trademark) ATN conc.", "MIKAWHITE MTN conc.", "MIKAWHITE KTN conc." “MIKAWHITE ACR” (trade name, manufactured by Nippon Kayaku), “Hakkol (registered trademark) PSR”, “Hakkol CHP-B”, “Hakkol PY-1800”, “Hakkol PY-2000”, “Hakkol HK” "Hakkol S-703" (trade name, manufactured by Hakkor Chemical), "Illuminal (registered trademark) EX conc.", "Illuminal CK conc." (Trade name, manufactured by Showa Kako) "Nikkafluor RP conc.", "Nikkafluor BP conc.", "Nikkafluor SB conc.", "Nikkafluor OB conc." (Trade name, manufactured by Japan Chemical Co., Ltd.) and the like.

  As the fluorescent pigment, those that are compatible with the resin are preferable. For example, magnesium, calcium, barium, strontium, aluminum, zinc, cadmium, and other oxides or sulfides with a trace amount of heavy metal or rare earth as an activator. Organic fluorescent pigments such as inorganic fluorescent pigments, various lumogen colors, thioflavine, rhodamine B, rhodamine 6G, and fluorescein dye, and those obtained by dissolving and powdering them in an organic resin can be used. Specifically, rumogen color (manufactured by BASF): 1,5-dianilinoanthracene (lumogen yellow), dianthylene (lumogen sea blue), sacylyl aldazine (lumogen yellow orange), 1,4-bis (β-cyano-β-carbo-ethoxyvinyl) benzene (Lumogen Bright Green), 2-anilino-4- (2,5-dichloro-benzoylamino) 1,9-anthra-pyrimidine (Lumogen) -Pigments such as reddish orange).

  As the inorganic pigment, those having an average particle diameter of 10 microns (μm) or less are preferable. For example, blue or violet pigments such as cobalt blue and cobalt violet are used. Specific examples include “ST-1218 violet”, “ST-5254 blue”, and “ST-5307 violet” (trade name, manufactured by Dainichi Seika Kogyo Co., Ltd.).

  These bluing agents may be used alone or in combination of two or more.

  Among these bluing agents, those of dye type are generally preferably used because they are generally highly soluble in monomers, and the transparency of the resulting resin and the lens made of the obtained resin is also increased.

The polymerizable composition of the present invention may further contain a thiol compound. In this case, in the compound represented by the general formula (1), m = 0 and X ₁ may be a sulfur atom. Further, at this time, m = 0, X ₁ may be a sulfur atom, n = p, and M may be a Sn atom.
Hereinafter, it describes about a thiol compound.

  The thiol compound used in the present invention is a compound containing one or more thiol groups (SH groups) in the molecule. As the thiol compound, for example, a compound having any structure can be used as long as it is compatible with the compound represented by the general formula (1).

As a thiol compound, specifically, as a monofunctional (monovalent) thiol compound, methyl mercaptan, ethyl mercaptan, propyl mercaptan, butyl mercaptan, octyl mercaptan, dodecyl mercaptan, tert-dodecyl mercaptan, hexadecyl mercaptan, octadecyl mercaptan , Cyclohexyl mercaptan, benzyl mercaptan, ethylphenyl mercaptan, 2-mercaptomethyl-1,3-dithiolane, 2-mercaptomethyl-1,4-dithiane, 1-mercapto-2,3-epithiopropane, 1-mercaptomethylthio- 2,3-epithiopropane, 1-mercaptoethylthio-2,3-epithiopropane, 3-mercaptothietane, 2-mercaptothietane, 3-mercaptomethylthiothie Down, 2-mercapto-methylthiazole punch line ethane, 3-mercapto-ethyl Ji punch line ethane, aliphatic mercaptan compounds such as 2-mercaptoethyl Ji punch line ethane;
Aromatic mercaptan compounds such as thiophenol and mercaptotoluene; and compounds containing hydroxy groups in addition to mercapto groups such as 2-mercaptoethanol and 3-mercapto-1,2-propanediol.

The polyfunctional thiol (polythiol) compound includes 1,1-methanedithiol, 1,2-ethanedithiol, 1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2 -Propanedithiol, 1,6-hexanedithiol, 1,2,3-propanetrithiol, 1,1-cyclohexanedithiol, 1,2-cyclohexanedithiol, 2,2-dimethylpropane-1,3-dithiol, 3, 4-dimethoxybutane-1,2-dithiol, 2-methylcyclohexane-2,3-dithiol, 1,1-bis (mercaptomethyl) cyclohexane, bis (2-mercaptoethyl ester) thiomalate, 2,3-dimercapto- 1-propanol (2-mercaptoacetate), 2,3-dimercap To-1-propanol (3-mercaptopropionate), diethylene glycol bis (2-mercaptoacetate), diethylene glycol bis (3-mercaptopropionate), 1,2-dimercaptopropyl methyl ether, 2,3-dimercapto Propyl methyl ether, 2,2-bis (mercaptomethyl) -1,3-propanedithiol, bis (2-mercaptoethyl) ether, ethylene glycol bis (2-mercaptoacetate), ethylene glycol bis (3-mercaptopropionate) ), Trimethylolpropane bis (2-mercaptoacetate), trimethylolpropane bis (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), tetrakis (mercaptomethyl) methane, 1,1,1,1- tetrakis (mercaptomethyl) aliphatic polythiol compounds such as methane;
1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis (mercaptomethyl) benzene, 1,3-bis (mercaptomethyl) benzene, 1,4- Bis (mercaptomethyl) benzene, 1,2-bis (mercaptoethyl) benzene, 1,3-bis (mercaptoethyl) benzene, 1,4-bis (mercaptoethyl) benzene, 1,2,3-trimercaptobenzene, 1,2,4-trimercaptobenzene, 1,3,5-trimercaptobenzene, 1,2,3-tris (mercaptomethyl) benzene, 1,2,4-tris (mercaptomethyl) benzene, 1,3,3 5-tris (mercaptomethyl) benzene, 1,2,3-tris (mercaptoethyl) benzene, 1,2,4-tris (mer Puttoethyl) benzene, 1,3,5-tris (mercaptoethyl) benzene, 2,5-toluenedithiol, 3,4-toluenedithiol, 1,3-di (p-methoxyphenyl) propane-2,2-dithiol, Aromatic polythiol compounds such as 1,3-diphenylpropane-2,2-dithiol, phenylmethane-1,1-dithiol, 2,4-di (p-mercaptophenyl) pentane;
1,2-bis (mercaptoethylthio) benzene, 1,3-bis (mercaptoethylthio) benzene, 1,4-bis (mercaptoethylthio) benzene, 1,2,3-tris (mercaptomethylthio) benzene, 1 , 2,4-Tris (mercaptomethylthio) benzene, 1,3,5-tris (mercaptomethylthio) benzene, 1,2,3-tris (mercaptoethylthio) benzene, 1,2,4-tris (mercaptoethylthio) ) Aromatic polythiol compounds containing sulfur atoms in addition to mercapto groups such as benzene, 1,3,5-tris (mercaptoethylthio) benzene, and their nuclear alkylated products;
Bis (mercaptomethyl) sulfide, bis (mercaptomethyl) disulfide, bis (mercaptoethyl) sulfide, bis (mercaptoethyl) disulfide, bis (mercaptopropyl) sulfide, bis (mercaptomethylthio) methane, bis (2-mercaptoethylthio) Methane, bis (3-mercaptopropylthio) methane, 1,2-bis (mercaptomethylthio) ethane, 1,2-bis (2-mercaptoethylthio) ethane, 1,2-bis (3-mercaptopropyl) ethane, 1,3-bis (mercaptomethylthio) propane, 1,3-bis (2-mercaptoethylthio) propane, 1,3-bis (3-mercaptopropylthio) propane, 1,2,3-tris (mercaptomethylthio) Propane, 1,2,3-tris (2- Lucaptoethylthio) propane, 1,2,3-tris (3-mercaptopropylthio) propane, 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane, 4,8-dimercaptomethyl -1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 5,7-dimercaptomethyl-1 , 11-dimercapto-3,6,9-trithiaundecane, tetrakis (mercaptomethylthiomethyl) methane, tetrakis (2-mercaptoethylthiomethyl) methane, tetrakis (3-mercaptopropylthiomethyl) methane, bis (2,3 -Dimercaptopropyl) sulfide, bis (1,3-dimercaptopropyl) sulfide, 2, Dimercapto-1,4-dithian, 2,5-bis (mercaptomethyl) -1,4-dithiane, 2,5-dimercaptomethyl-2,5-dimethyl-1,4-dithiane, bis (mercaptomethyl) Aliphatic polythiol compounds containing sulfur atoms in addition to mercapto groups such as disulfide, bis (mercaptoethyl) disulfide, bis (mercaptopropyl) disulfide, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, and the like Thioglycolic acid and mercaptopropionic acid esters;
Hydroxymethyl sulfide bis (2-mercaptoacetate), hydroxymethyl sulfide bis (3-mercaptopropionate), hydroxyethyl sulfide bis (2-mercaptoacetate), hydroxyethyl sulfide bis (3-mercaptopropionate), hydroxypropyl Sulfide bis (2-mercaptoacetate), hydroxypropyl sulfide bis (3-mercaptopropionate), hydroxymethyl disulfide bis (2-mercaptoacetate), hydroxymethyl disulfide bis (3-mercaptopropionate), hydroxyethyl disulfide bis (2-mercaptoacetate), hydroxyethyl disulfide bis (3-mercaptopropionate), hydroxypropyl disulfide bis 2-mercaptoacetate), hydroxypropyl disulfide bis (3-mercaptopropionate), 2-mercaptoethyl ether bis (2-mercaptoacetate), 2-mercaptoethyl ether bis (3-mercaptopropionate), 1,4 Dithian-2,5-diol bis (2-mercaptoacetate), 1,4-dithian-2,5-diol bis (3-mercaptopropionate), thiodiglycolic acid bis (2-mercaptoethyl ester), thiodi Propionic acid bis (2-mercaptoethyl ester), 4,4-thiodibutyric acid bis (2-mercaptoethyl ester), dithiodiglycolic acid bis (2-mercaptoethyl ester), dithiodipropionic acid bis (2-mercaptoethyl ester) ), 4,4-dithio Dibutyl acid bis (2-mercaptoethyl ester), thiodiglycolic acid bis (2,3-dimercaptopropyl ester), thiodipropionic acid bis (2,3-dimercaptopropyl ester), dithioglycolic acid bis (2, An aliphatic polythiol compound containing a sulfur atom and an ester bond in addition to a mercapto group such as 3-dimercaptopropyl ester) and bis (2,3-dimercaptopropyl ester) dithiodipropionate;
Heterocyclic compounds containing sulfur atoms in addition to mercapto groups such as 3,4-thiophenedithiol and 2,5-dimercapto-1,3,4-thiadiazole;
Glycerin di (mercaptoacetate), 1-hydroxy-4-mercaptocyclohexane, 2,4-dimercaptophenol, 2-mercaptohydroquinone, 4-mercaptophenol, 3,4-dimercapto-2-propanol, 1,3-dimercapto- 2-propanol, 2,3-dimercapto-1-propanol, 1,2-dimercapto-1,3-butanediol, pentaerythritol tris (3-mercaptopropionate), pentaerythritol mono (3-mercaptopropionate) Pentaerythritol bis (3-mercaptopropionate), pentaerythritol tris (thioglycolate), dipentaerythritol pentakis (3-mercaptopropionate), hydroxymethyl-tris (mercaptoeth) Ruchiomechiru) methane, compounds containing 1-hydroxyethyl-thio-3-mercaptoethyl hydroxy group other than the mercapto group of thio benzene;
1,1,3,3-tetrakis (mercaptomethylthio) propane, 1,1,2,2-tetrakis (mercaptomethylthio) ethane, 4,6-bis (mercaptomethylthio) -1,3-dithiane, 4,6- Bis (mercaptomethylthio) -1,3-dithiacyclohexane, 1,1,5,5-tetrakis (mercaptomethylthio) -3-thiapentane, 1,1,6,6-tetrakis (mercaptomethylthio) -3,4- Dithiahexane, 2,2-bis (mercaptomethylthio) ethanethiol, 2- (4,5-dimercapto-2-thiapentyl) -1,3-dithiacyclopentane, 2,2-bis (mercaptomethyl) -1,3 -Dithiacyclopentane, 2,5-bis (4,4-bis (mercaptomethylthio) -2-thiabutyl) -1,4-dithia 2,2-bis (mercaptomethylthio) -1,3-propanedithiol, 3-mercaptomethylthio-1,7-dimercapto-2,6-dithiaheptane, 3,6-bis (mercaptomethylthio) -1,9-dimercapto -2,5,8-trithianonane, 4,6-bis (mercaptomethylthio) -1,9-dimercapto-2,5,8-trithianonane, 3-mercaptomethylthio-1,6-dimercapto-2,5-dithiahexane, 2- (2,2-bis (mercaptomethylthio) ethyl) -1,3-dithietane, 1,1,9,9-tetrakis (mercaptomethylthio) -5- (3,3-bis (mercaptomethylthio) -1- Thiapropyl) 3,7-dithianonane, tris (2,2-bis (mercaptomethylthio) ethyl) methane, tris ( , 4-bis (mercaptomethylthio) -2-thiabutyl) methane, tetrakis (2,2-bis (mercaptomethylthio) ethyl) methane, tetrakis (4,4-bis (mercaptomethylthio) -2-thiabutyl) methane, 5,9,11-tetrakis (mercaptomethylthio) -1,13-dimercapto-2,6,8,12-tetrathiatridecane, 3,5,9,11,15,17-hexakis (mercaptomethylthio) -1 , 19-dimercapto-2,6,8,12,14,18-hexathiononadecane, 9- (2,2-bis (mercaptomethylthio) ethyl) -3,5,13,15-tetrakis (mercaptomethylthio) -1,17-dimercapto-2,6,8,10,12,16-hexathiaheptadecane, 3,4,8,9-tetra Kis (mercaptomethylthio) -1,11-dimercapto-2,5,7,10-tetrathiaundecane, 3,4,8,9,13,14-hexakis (mercaptomethylthio) -1,16-dimercapto-2, 5,7,10,12,15-hexathiahexadecane, 8- {bis (mercaptomethylthio) methyl} -3,4,12,13-tetrakis (mercaptomethylthio) -1,15-dimercapto-2,5,7 , 9,11,14-hexathiapentadecane, 4,6-bis {3,5-bis (mercaptomethylthio) -7-mercapto-2,6-dithiaheptylthio} -1,3-dithiane, 4- { 3,5-bis (mercaptomethylthio) -7-mercapto-2,6-dithiaheptylthio} -6-mercaptomethylthio-1,3-dithiane, 1, -Bis {4- (6-mercaptomethylthio) -1,3-dithianylthio} -3,3-bis (mercaptomethylthio) propane, 1,3-bis {4- (6-mercaptomethylthio) -1,3-dithianylthio } -1,3-bis (mercaptomethylthio) propane, 1- {4- (6-mercaptomethylthio) -1,3-dithianylthio} -3- {2,2-bis (mercaptomethylthio) ethyl} -7,9 -Bis (mercaptomethylthio) -2,4,6,10-tetrathiaundecane, 1- {4- (6-mercaptomethylthio) -1,3-dithianylthio} -3- {2- (1,3-dithietanyl) } Methyl-7,9-bis (mercaptomethylthio) -2,4,6,10-tetrathiaundecane, 1,5-bis {4- (6-mercaptomethylthio) 1,3-dithianylthio} -3- {2- (1,3-dithietanyl)} methyl-2,4-dithiapentane, 4,6-bis [3- {2- (1,3-dithietanyl)} methyl-5 -Mercapto-2,4-dithiapentylthio] -1,3-dithiane, 4,6-bis {4- (6-mercaptomethylthio) -1,3-dithianylthio} -1,3-dithiane, 4- { 4- (6-mercaptomethylthio) -1,3-dithianylthio} -6- {4- (6-mercaptomethylthio) -1,3-dithianylthio} -1,3-dithiane, 3- {2- (1,3 -Dithietanyl)} methyl-7,9-bis (mercaptomethylthio) -1,11-dimercapto-2,4,6,10-tetrathiaundecane, 9- {2- (1,3-dithietanyl)} methyl-3 , 5, 13, 15 -Tetrakis (mercaptomethylthio) -1,17-dimercapto-2,6,8,10,12,16-hexathiaheptadecane, 3- {2- (1,3-dithietanyl)} methyl-7,9,13 , 15-tetrakis (mercaptomethylthio) -1,17-dimercapto-2,4,6,10,12,16-hexathiaheptadecane, 3,7-bis {2- (1,3-dithietanyl)} methyl- 1,9-dimercapto-2,4,6,8-tetrathianonane, 4- {3,4,8,9-tetrakis (mercaptomethylthio) -11-mercapto-2,5,7,10-tetrathiaun Decyl} -5-mercaptomethylthio-1,3-dithiolane, 4,5-bis {3,4-bis (mercaptomethylthio) -6-mercapto-2,5-dithiahexylthio} -1 3-dithiolane, 4- {3,4-bis (mercaptomethylthio) -6-mercapto-2,5-dithiahexylthio} -5-mercaptomethylthio-1,3-dithiolane, 4- {3-bis (mercapto) Methylthio) methyl-5,6-bis (mercaptomethylthio) -8-mercapto-2,4,7-trithiaoctyl} -5-mercaptomethylthio-1,3-dithiolane, 2- [bis {3,4-bis (Mercaptomethylthio) -6-mercapto-2,5-dithiahexylthio} methyl] -1,3-dithietane, 2- {3,4-bis (mercaptomethylthio) -6-mercapto-2,5-dithia Hexylthio} mercaptomethylthiomethyl-1,3-dithietane, 2- {3,4,8,9-tetrakis (mercaptomethylthio) -11-mercapto 2,5,7,10-tetrathiaundecylthio} mercaptomethylthiomethyl-1,3-dithietane, 2- {3-bis (mercaptomethylthio) methyl-5,6-bis (mercaptomethylthio) -8-mercapto- 2,4,7-trithiaoctyl} mercaptomethylthiomethyl-1,3-dithietane, 4,5-bis [1- {2- (1,3-dithietanyl)}-3-mercapto-2-thiapropylthio] -1,3-dithiolane, 4- [1- {2- (1,3-dithietanyl)}-3-mercapto-2-thiapropylthio] -5- {1,2-bis (mercaptomethylthio) -4- Mercapto-3-thiabutylthio} -1,3-dithiolane, 2- [bis {4- (5-mercaptomethylthio-1,3-dithiolanyl) thio}] methyl-1,3-dithieta 4- {4- (5-mercaptomethylthio-1,3-dithiolanyl) thio} -5- [1- {2- (1,3-dithietanyl)}-3-mercapto-2-thiapropylthio]- Compounds having a dithioacetal or dithioketal skeleton such as 1,3-dithiolane and oligomers thereof;
Tris (mercaptomethylthio) methane, tris (mercaptoethylthio) methane, 1,1,5,5-tetrakis (mercaptomethylthio) -2,4-dithiapentane, bis [4,4-bis (mercaptomethylthio) -1,3 -Dithiabutyl] (mercaptomethylthio) methane, tris [4,4-bis (mercaptomethylthio) -1,3-dithiabutyl] methane, 2,4,6-tris (mercaptomethylthio) -1,3,5-trithiacyclohexane 2,4-bis (mercaptomethylthio) -1,3,5-trithiacyclohexane, 1,1,3,3-tetrakis (mercaptomethylthio) -2-thiapropane, bis (mercaptomethyl) methylthio-1,3 5-trithiacyclohexane, tris [(4-mercaptomethyl-2,5-dithi Cyclohexyl-1-yl) methylthio] methane, 2,4-bis (mercaptomethylthio) -1,3-dithiacyclopentane, 2-mercaptoethylthio-4-mercaptomethyl-1,3-dithiacyclopentane, 2 -(2,3-dimercaptopropylthio) -1,3-dithiacyclopentane, 4-mercaptomethyl-2- (2,3-dimercaptopropylthio) -1,3-dithiacyclopentane, 4- Mercaptomethyl-2- (1,3-dimercapto-2-propylthio) -1,3-dithiacyclopentane, tris [2,2-bis (mercaptomethylthio) -1-thiaethyl] methane, tris [3,3- Bis (mercaptomethylthio) -2-thiapropyl] methane, tris [4,4-bis (mercaptomethylthio) -3-thiabutyl] me 2,4,6-tris [3,3-bis (mercaptomethylthio) -2-thiapropyl] -1,3,5-trithiacyclohexane, tetrakis [3,3-bis (mercaptomethylthio) -2-thiapropyl ] Compounds having an ortho trithioformate skeleton such as methane and the like; and 3,3′-di (mercaptomethylthio) -1,5-dimercapto-2,4-dithiapentane, 2,2′-di (mercapto) Methylthio) -1,3-dithiacyclopentane, 2,7-di (mercaptomethyl) -1,4,5,9-tetrathiaspiro [4,4] nonane, 3,9-dimercapto-1,5 Examples include 7,11-tetrathiaspiro [5,5] undecane, and compounds having an orthotetrathiocarbonate skeleton such as oligomers thereof. It is, but is not limited to these exemplified compounds. These exemplary compounds may be used alone or in combination of two or more.

  Of these thiol compounds, it is preferable to select an aliphatic thiol compound rather than an aromatic one in consideration of the optical properties of the resulting resin, particularly the Abbe number. Further, in view of optical properties, particularly the requirement for refractive index, it is more preferable to select a compound having a sulfur atom in addition to a thiol group such as a sulfide bond and / or a disulfide bond. In order to increase the three-dimensional crosslinkability in consideration of the heat resistance of the resulting resin, it is particularly preferable to select one or more thiol compounds having a polymerizable group such as an epithio group or a thietanyl group or compounds having three or more thiol groups. preferable.

  Further, from the viewpoint of improving the balance between the refractive index and the mechanical properties, it is preferable to use a thiol compound having a thietane ring.

  Preferred thiols from the above viewpoint include 1-mercapto-2,3-epithiopropane, 1-mercaptomethylthio-2,3-epithiopropane, 1-mercaptoethylthio-2,3-epithiopropane, 3- Mercaptothietane, 2-mercaptothietane, 3-mercaptomethylthiothietane, 2-mercaptomethylthiothietane, 3-mercaptoethylthiothietane, 2-mercaptoethylthiothietane, 2,5-bis (mercaptomethyl)- 1,4-dithiane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7 Dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 5,7-di Lucaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 1,1,1,1-tetrakis (mercaptomethyl) methane, 1,1,3,3-tetrakis (mercaptomethylthio) propane, 1, 1,2,2-tetrakis (mercaptomethylthio) ethane, 4,6-bis (mercaptomethylthio) -1,3-dithiane, 2- (2,2-bis (mercaptomethylthio) ethyl) -1,3-dithietane is there.

  More preferably, 3-mercaptothietane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, , 1,1,1-tetrakis (mercaptomethyl) methane, 1,1,3,3-tetrakis (mercaptomethylthio) propane, 1,1,2,2-tetrakis (mercaptomethylthio) ethane, 4,6-bis ( Mercaptomethylthio) -1,3-dithiane, 2- (2,2-bis (mercaptomethylthio) ethyl) -1,3-dithietane, 2, - bis (mercaptomethyl) -1,4-a-dithiane. Moreover, when selecting a bivalent thiol compound, it is preferable to use it mixing with the thiol compound which has a polymeric group, and / or the trivalent or more thiol compound.

More specifically, the thiol compound is 3-mercaptothietane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6. , 9-trithiaundecane and 2,5-bis (mercaptomethyl) -1,4-dithiane.
Moreover, as a preferable combination of a thiol compound and the compound represented by the said General formula (1), the following are mentioned, for example.
(I) In the compound represented by the general formula (1), n = p, m = 0, X ₁ is a sulfur atom, and the thiol compound is 3-mercaptothietane, 4-mercaptomethyl-1, From 8-dimercapto-3,6-dithiaoctane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane and 2,5-bis (mercaptomethyl) -1,4-dithiane A combination of one or more selected from the group consisting of: 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaun Kang and 2,5-bis (mercaptomethyl) -1,4-combination is at least one selected from the group consisting of dithiane.

  As the amount of these thiol compounds used, when the total amount of the compound represented by the general formula (1) and the thiol compound is 100 parts by weight, if the amount of the thiol compound used is too small, the mechanical strength and the yellowness are improved. May be low and unfavorable. In addition, when the total amount of the compound represented by the general formula (1) and the thiol compound is 100 parts by weight, if the amount of the thiol compound used is too large, a decrease in heat resistance may be extremely undesirable.

  Therefore, the amount of the thiol compound used is preferably 1 part by weight or more and 50 parts by weight or less when the total of the compound represented by the general formula (1) and the thiol compound is 100 parts by weight. More preferably, the amount of the thiol compound used is 1 part by weight or more and 25 parts by weight or less when the total of the compound represented by the general formula (1) and the thiol compound is 100 parts by weight.

The polymerizable composition of the present invention may further contain an epoxy compound and / or an episulfide compound. In this case, in the compound represented by the general formula (1), m = 0 and X ₁ may be a sulfur atom. Further, at this time, m = 0, X ₁ may be a sulfur atom, n = p, and M may be a Sn atom.

  Epoxy compounds and episulfide compounds each contain one or more epoxy groups and episulfide groups in the molecule. The epoxy compound and episulfide compound may be any compound having any structure as long as it is compatible with the compound represented by the above general formula (1). Preferably, the epoxy group and / or the episulfide group are combined. It is a compound containing two or more.

Specifically, as an epoxy compound, a phenolic epoxy compound (for example, bisphenol A glycidyl ether, bisphenol F glycidyl ether) obtained by a condensation reaction of a polyhydric phenol compound such as bisphenol A or bisphenol F and an epihalohydrin compound;
Alcohol-based epoxy compounds obtained by condensation of polyhydric alcohol compounds such as hydrogenated bisphenol A, hydrogenated bisphenol F, and cyclohexanedimethanol with epihalohydrin compounds (for example, hydrogenated bisphenol A glycidyl ether, hydrogenated bisphenol F glycidyl ether) ;
Glycidyl ester system obtained by condensation of polyvalent organic acid compound and epihalohydrin compound such as 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate and 1,2-hexahydrophthalic acid diglycidyl ester And epoxy compounds; and amine-based epoxy compounds obtained by condensation of primary and secondary amine compounds with epihalohydrin compounds. Other examples include aliphatic polyvalent epoxy compounds such as vinylcyclohexene diepoxide such as 4-vinyl-1-cyclohexane diepoxide.

Specific examples of the sulfide group-containing epoxy compound and the ether group-containing epoxy compound include bis (2,3-epoxypropyl) sulfide, bis (2,3-epoxypropyl) disulfide, and bis (2,3-epoxypropylthio). ) Methane, 1,2-bis (2,3-epoxypropylthio) ethane, 1,2-bis (2,3-epoxypropylthio) propane, 1,3-bis (2,3-epoxypropylthio) propane 1,3-bis (2,3-epoxypropylthio) -2-methylpropane, 1,4-bis (2,3-epoxypropylthio) butane, 1,4-bis (2,3-epoxypropylthio) ) -2-Methylbutane, 1,3-bis (2,3-epoxypropylthio) butane, 1,5-bis (2,3-epoxypropylthio) pentane 1,5-bis (2,3-epoxypropylthio) -2-methylpentane, 1,5-bis (2,3-epoxypropylthio) -3-thiapentane, 1,6-bis (2,3-epoxy Propylthio) hexane, 1,6-bis (2,3-epoxypropylthio) -2-methylhexane, 3,8-bis (2,3-epoxypropylthio) -3,6-dithiaoctane, 1,2, 3-tris (2,3-epoxypropylthio) propane, 2,2-bis (2,3-epoxypropylthio) -1,3-bis (2,3-epoxypropylthiomethyl) propane, 2,2- Bis (2,3-epoxypropylthiomethyl) -1- (2,3-epoxypropylthio) butane, 1,5-bis (2,3-epoxypropylthio) -2- (2,3-epoxypropylthio) Me L) -3-thiapentane, 1,5-bis (2,3-epoxypropylthio) -2,4-bis (2,3-epoxypropylthiomethyl) -3-thiapentane, 1- (2,3-epoxy Propylthio) -2,2-bis (2,3-epoxypropylthiomethyl) -4-thiahexane, 1,5,6-tris (2,3-epoxypropylthio) -4- (2,3-epoxypropyl) Thiomethyl) -3-thiahexane, 1,8-bis (2,3-epoxypropylthio) -4- (2,3-epoxypropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (2, 3-epoxypropylthio) -4,5-bis (2,3-epoxypropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (2,3-epoxypropylthio) -4,4-bis ( 2,3- Epoxypropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (2,3-epoxypropylthio) -2,5-bis (2,3-epoxypropylthiomethyl) -3,6-dithiaoctane, , 8-bis (2,3-epoxypropylthio) -2,4,5-tris (2,3-epoxypropylthiomethyl) -3,6-dithiaoctane, 1,1,1-tris [[2- ( 2,3-epoxypropylthio) ethyl] thiomethyl] -2- (2,3-epoxypropylthio) ethane, 1,1,2,2-tetrakis [[2- (2,3-epoxypropylthio) ethyl] Thiomethyl] ethane, 1,11-bis (2,3-epoxypropylthio) -4,8-bis (2,3-epoxypropylthiomethyl) -3,6,9-trithiaundecane, 1,11-bi (2,3-epoxypropylthio) -4,7-bis (2,3-epoxypropylthiomethyl) -3,6,9-trithiaundecane, 1,11-bis (2,3-epoxypropylthio) Chain aliphatic 2,3-epoxypropylthio compounds such as -5,7-bis (2,3-epoxypropylthiomethyl) -3,6,9-trithiaundecane;
1,3-bis (2,3-epoxypropylthio) cyclohexane, 1,4-bis (2,3-epoxypropylthio) cyclohexane, 1,3-bis (2,3-epoxypropylthiomethyl) cyclohexane, 1 , 4-bis (2,3-epoxypropylthiomethyl) cyclohexane, 2,5-bis (2,3-epoxypropylthiomethyl) -1,4-dithiane, 2,5-bis [[2- (2, Cyclic epoxy such as 3-epoxypropylthio) ethyl] thiomethyl] -1,4-dithiane, 2,5-bis (2,3-epoxypropylthiomethyl) -2,5-dimethyl-1,4-dithiane 2,3-epoxypropylthio compound;
1,2-bis (2,3-epoxypropylthio) benzene, 1,3-bis (2,3-epoxypropylthio) benzene, 1,4-bis (2,3-epoxypropylthio) benzene, 1, 2-bis (2,3-epoxypropylthiomethyl) benzene, 1,3-bis (2,3-epoxypropylthiomethyl) benzene, 1,4-bis (2,3-epoxypropylthiomethyl) benzene, bis [4- (2,3-epoxypropylthio) phenyl] methane, 2,2-bis [4- (2,3-epoxypropylthio) phenyl] propane, bis [4- (2,3-epoxypropylthio) Aromatic 2 such as phenyl] sulfide, bis [4- (2,3-epoxypropylthio) phenyl] sulfone, 4,4′-bis (2,3-epoxypropylthio) biphenyl , 3-epoxypropylthio compounds;
Monofunctional epoxy compounds such as ethylene oxide, propylene oxide, glycidol, epichlorohydrin;
Bis (2,3-epoxypropyl) ether, bis (2,3-epoxypropyloxy) methane, 1,2-bis (2,3-epoxypropyloxy) ethane, 1,2-bis (2,3-epoxy) Propyloxy) propane, 1,3-bis (2,3-epoxypropyloxy) propane, 1,3-bis (2,3-epoxypropyloxy) -2-methylpropane, 1,4-bis (2,3 -Epoxypropyloxy) butane, 1,4-bis (2,3-epoxypropyloxy) -2-methylbutane, 1,3-bis (2,3-epoxypropyloxy) butane, 1,5-bis (2, 3-epoxypropyloxy) pentane, 1,5-bis (2,3-epoxypropyloxy) -2-methylpentane, 1,5-bis (2,3-epoxypropyloxy) 3-thiapentane, 1,6-bis (2,3-epoxypropyloxy) hexane, 1,6-bis (2,3-epoxypropyloxy) -2-methylhexane, 3,8-bis (2,3- Epoxypropyloxy) -3,6-dithiaoctane, 1,2,3-tris (2,3-epoxypropyloxy) propane, 2,2-bis (2,3-epoxypropyloxy) -1,3-bis ( 2,3-epoxypropyloxymethyl) propane, 2,2-bis (2,3-epoxypropyloxymethyl) -1- (2,3-epoxypropyloxy) butane, 1,5-bis (2,3- Epoxypropyloxy) -2- (2,3-epoxypropyloxymethyl) -3-thiapentane, 1,5-bis (2,3-epoxypropyloxy) -2,4-bis (2, -Epoxypropyloxymethyl) -3-thiapentane, 1- (2,3-epoxypropyloxy) -2,2-bis (2,3-epoxypropyloxymethyl) -4-thiahexane, 1,5,6-tris (2,3-epoxypropyloxy) -4- (2,3-epoxypropyloxymethyl) -3-thiahexane, 1,8-bis (2,3-epoxypropyloxy) -4- (2,3-epoxy Propyloxymethyl) -3,6-dithiaoctane, 1,8-bis (2,3-epoxypropyloxy) -4,5-bis (2,3-epoxypropyloxymethyl) -3,6-dithiaoctane, 1, 8-bis (2,3-epoxypropyloxy) -4,4-bis (2,3-epoxypropyloxymethyl) -3,6-dithiaoctane, 1,8-bis ( 2,3-epoxypropyloxy) -2,5-bis (2,3-epoxypropyloxymethyl) -3,6-dithiaoctane, 1,8-bis (2,3-epoxypropyloxy) -2,4 5-tris (2,3-epoxypropyloxymethyl) -3,6-dithiaoctane, 1,1,1-tris [[2- (2,3-epoxypropyloxy) ethyl] thiomethyl] -2- (2, 3-epoxypropyloxy) ethane, 1,1,2,2-tetrakis [[2- (2,3-epoxypropyloxy) ethyl] thiomethyl] ethane, 1,11-bis (2,3-epoxypropyloxy) -4,8-bis (2,3-epoxypropyloxymethyl) -3,6,9-trithiaundecane, 1,11-bis (2,3-epoxypropyloxy) -4,7-bis 2,3-epoxypropyloxymethyl) -3,6,9-trithiaundecane, 1,11-bis (2,3-epoxypropyloxy) -5,7-bis (2,3-epoxypropyloxymethyl) A chain aliphatic 2,3-epoxypropyloxy compound such as -3,6,9-trithiaundecane;
1,3-bis (2,3-epoxypropyloxy) cyclohexane, 1,4-bis (2,3-epoxypropyloxy) cyclohexane, 1,3-bis (2,3-epoxypropyloxymethyl) cyclohexane, 1 , 4-bis (2,3-epoxypropyloxymethyl) cyclohexane, 2,5-bis (2,3-epoxypropyloxymethyl) -1,4-dithiane, 2,5-bis [[2- (2, Cyclic epoxy such as 3-epoxypropyloxy) ethyl] thiomethyl] -1,4-dithiane, 2,5-bis (2,3-epoxypropyloxymethyl) -2,5-dimethyl-1,4-dithiane A 2,3-epoxypropyloxy compound; and
1,2-bis (2,3-epoxypropyloxy) benzene, 1,3-bis (2,3-epoxypropyloxy) benzene, 1,4-bis (2,3-epoxypropyloxy) benzene, 1, 2-bis (2,3-epoxypropyloxymethyl) benzene, 1,3-bis (2,3-epoxypropyloxymethyl) benzene, 1,4-bis (2,3-epoxypropyloxymethyl) benzene, bis [4- (2,3-epoxypropyloxy) phenyl] methane, 2,2-bis [4- (2,3-epoxypropyloxy) phenyl] propane, bis [4- (2,3-epoxypropyloxy) Phenyl] sulfide, bis [4- (2,3-epoxypropyloxy) phenyl] sulfone, 4,4′-bis (2,3-epoxypropyloxy) Examples include aromatic 2,3-epoxypropyloxy compounds such as biphenyl, but are not limited to the exemplified compounds.

Of these exemplified epoxy compounds, preferably bis (2,3-epoxypropyl) disulfide;
4-vinyl-1-cyclohexane diepoxide;
A phenolic epoxy compound (for example, bisphenol A glycidyl ether, bisphenol F glycidyl ether) obtained by a condensation reaction of a polyhydric phenol compound such as bisphenol A or bisphenol F and an epihalohydrin compound;
Alcohol-based epoxy compounds obtained by condensation of polyhydric alcohol compounds such as hydrogenated bisphenol A and hydrogenated bisphenol F and epihalohydrin compounds (for example, hydrogenated bisphenol A glycidyl ether, hydrogenated bisphenol F glycidyl ether);
3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate;
A glycidyl ester epoxy compound obtained by condensation of a polyvalent organic acid compound such as 1,2-hexahydrophthalic acid diglycidyl ester and an epihalohydrin compound;
Examples thereof include amine-based epoxy compounds obtained by condensation of primary and secondary diamine compounds and epihalohydrin compounds. In addition, other examples include aliphatic polyvalent epoxy compounds such as vinylcyclohexene diepoxide.
More preferably, bis (2,3-epoxypropyl) disulfide, 1,3-bis (2,3-epoxypropyloxy) cyclohexane (ie, cyclohexanedimethanol diglycidyl ether), bisphenol A glycidyl ether, bisphenol F glycidyl ether is there. More preferred are cyclohexanedimethanol diglycidyl ether and bisphenol F glycidyl ether.

Specific examples of the episulfide compound include bis (1,2-epithioethyl) sulfide, bis (1,2-epithioethyl) disulfide, bis (epithioethylthio) methane, bis (epithioethylthio) benzene, and bis [4. Epithioethylthio compounds such as-(epithioethylthio) phenyl] sulfide, bis [4- (epithioethylthio) phenyl] methane;
Bis (2,3-epithiopropyl) sulfide, bis (2,3-epithiopropyl) disulfide, bis (2,3-epithiopropylthio) methane, 1,2-bis (2,3-epithiopropyl) Thio) ethane, 1,2-bis (2,3-epithiopropylthio) propane, 1,3-bis (2,3-epithiopropylthio) propane, 1,3-bis (2,3-epithio) Propylthio) -2-methylpropane, 1,4-bis (2,3-epithiopropylthio) butane, 1,4-bis (2,3-epithiopropylthio) -2-methylbutane, 1,3- Bis (2,3-epithiopropylthio) butane, 1,5-bis (2,3-epithiopropylthio) pentane, 1,5-bis (2,3-epithiopropylthio) -2-methylpentane 1,5-bis (2, -Epithiopropylthio) -3-thiapentane, 1,6-bis (2,3-epithiopropylthio) hexane, 1,6-bis (2,3-epithiopropylthio) -2-methylhexane, 3, , 8-bis (2,3-epithiopropylthio) -3,6-dithiaoctane, 1,2,3-tris (2,3-epithiopropylthio) propane, 2,2-bis (2,3- Epithiopropylthio) -1,3-bis (2,3-epithiopropylthiomethyl) propane, 2,2-bis (2,3-epithiopropylthiomethyl) -1- (2,3-epithio Propylthio) butane, 1,5-bis (2,3-epithiopropylthio) -2- (2,3-epithiopropylthiomethyl) -3-thiapentane, 1,5-bis (2,3-epi Thiopropylthio) -2,4-bis ( , 3-epithiopropylthiomethyl) -3-thiapentane, 1- (2,3-epithiopropylthio) -2,2-bis (2,3-epithiopropylthiomethyl) -4-thiahexane, 1, 5,6-Tris (2,3-epithiopropylthio) -4- (2,3-epithiopropylthiomethyl) -3-thiahexane, 1,8-bis (2,3-epithiopropylthio)- 4- (2,3-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (2,3-epithiopropylthio) -4,5-bis (2,3-epithiopropylthio) Methyl) -3,6-dithiaoctane, 1,8-bis (2,3-epithiopropylthio) -4,4-bis (2,3-epithiopropylthiomethyl) -3,6-dithiaoctane, 1, 8-bis (2,3-epithiop Lopyrthio) -2,5-bis (2,3-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (2,3-epithiopropylthio) -2,4,5-tris ( 2,3-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,1,1-tris [[2- (2,3-epithiopropylthio) ethyl] thiomethyl] -2- (2,3- Epithiopropylthio) ethane, 1,1,2,2-tetrakis [[2- (2,3-epithiopropylthio) ethyl] thiomethyl] ethane, 1,11-bis (2,3-epithiopropylthio) ) -4,8-bis (2,3-epithiopropylthiomethyl) -3,6,9-trithiaundecane, 1,11-bis (2,3-epithiopropylthio) -4,7-bis (2,3-epithiopropylthiomethyl) 3,6,9-trithiaundecane, 1,11-bis (2,3-epithiopropylthio) -5,7-bis (2,3-epithiopropylthiomethyl) -3,6,9-tri Chain aliphatic 2,3-epithiopropylthio compounds such as thiaundecane;
1,3-bis (2,3-epithiopropylthio) cyclohexane, 1,4-bis (2,3-epithiopropylthio) cyclohexane, 1,3-bis (2,3-epithiopropylthiomethyl) Cyclohexane, 1,4-bis (2,3-epithiopropylthiomethyl) cyclohexane, 2,5-bis (2,3-epithiopropylthiomethyl) -1,4-dithiane, 2,5-bis [[ 2- (2,3-epithiopropylthio) ethyl] thiomethyl] -1,4-dithiane, 2,5-bis (2,3-epithiopropylthiomethyl) -2,5-dimethyl-1,4- Cycloaliphatic 2,3-epithiopropylthio compounds such as dithiane;
1,2-bis (2,3-epithiopropylthio) benzene, 1,3-bis (2,3-epithiopropylthio) benzene, 1,4-bis (2,3-epithiopropylthio) benzene 1,2-bis (2,3-epithiopropylthiomethyl) benzene, 1,3-bis (2,3-epithiopropylthiomethyl) benzene, 1,4-bis (2,3-epithiopropyl) Thiomethyl) benzene, bis [4- (2,3-epithiopropylthio) phenyl] methane, 2,2-bis [4- (2,3-epithiopropylthio) phenyl] propane, bis [4- ( 2,3-epithiopropylthio) phenyl] sulfide, bis [4- (2,3-epithiopropylthio) phenyl] sulfone, 4,4′-bis (2,3-epithiopropylthio) biphenyl, etc. Aromatic 2 , 3-epithiopropylthio compound;
Monofunctional episulfide compounds (compounds having one episulfide group) such as ethylene sulfide, propylene sulfide, mercaptopropylene sulfide, mercaptobutene sulfide, epithiochlorohydrin;
Bis (2,3-epithiopropyl) ether, bis (2,3-epithiopropyloxy) methane, 1,2-bis (2,3-epithiopropyloxy) ethane, 1,2-bis (2, 3-epithiopropyloxy) propane, 1,3-bis (2,3-epithiopropyloxy) propane, 1,3-bis (2,3-epithiopropyloxy) -2-methylpropane, 1,4 -Bis (2,3-epithiopropyloxy) butane, 1,4-bis (2,3-epithiopropyloxy) -2-methylbutane, 1,3-bis (2,3-epithiopropyloxy) butane 1,5-bis (2,3-epithiopropyloxy) pentane, 1,5-bis (2,3-epithiopropyloxy) -2-methylpentane, 1,5-bis (2,3-epi Thiopropyloxy) 3-thiapentane, 1,6-bis (2,3-epithiopropyloxy) hexane, 1,6-bis (2,3-epithiopropyloxy) -2-methylhexane, 3,8-bis (2, 3-epithiopropyloxy) -3,6-dithiaoctane, 1,2,3-tris (2,3-epithiopropyloxy) propane, 2,2-bis (2,3-epithiopropyloxy) -1 , 3-bis (2,3-epithiopropyloxymethyl) propane, 2,2-bis (2,3-epithiopropyloxymethyl) -1- (2,3-epithiopropyloxy) butane, 1, 5-bis (2,3-epithiopropyloxy) -2- (2,3-epithiopropyloxymethyl) -3-thiapentane, 1,5-bis (2,3-epithiopropyloxy) -2, 4-bis (2, -Epithiopropyloxymethyl) -3-thiapentane, 1- (2,3-epithiopropyloxy) -2,2-bis (2,3-epithiopropyloxymethyl) -4-thiahexane, 1,5, 6-Tris (2,3-epithiopropyloxy) -4- (2,3-epithiopropyloxymethyl) -3-thiahexane, 1,8-bis (2,3-epithiopropyloxy) -4- (2,3-epithiopropyloxymethyl) -3,6-dithiaoctane, 1,8-bis (2,3-epithiopropyloxy) -4,5-bis (2,3-epithiopropyloxymethyl) 3,6-dithiaoctane, 1,8-bis (2,3-epithiopropyloxy) -4,4-bis (2,3-epithiopropyloxymethyl) -3,6-dithiaoctane, 1,8- Screw( 2,3-epithiopropyloxy) -2,5-bis (2,3-epithiopropyloxymethyl) -3,6-dithiaoctane, 1,8-bis (2,3-epithiopropyloxy) -2 , 4,5-tris (2,3-epithiopropyloxymethyl) -3,6-dithiaoctane, 1,1,1-tris [[2- (2,3-epithiopropyloxy) ethyl] thiomethyl]- 2- (2,3-epithiopropyloxy) ethane, 1,1,2,2-tetrakis [[2- (2,3-epithiopropyloxy) ethyl] thiomethyl] ethane, 1,11-bis (2 , 3-epithiopropyloxy) -4,8-bis (2,3-epithiopropyloxymethyl) -3,6,9-trithiaundecane, 1,11-bis (2,3-epithiopropyloxy) ) -4,7-Bis 2,3-epithiopropyloxymethyl) -3,6,9-trithiaundecane, 1,11-bis (2,3-epithiopropyloxy) -5,7-bis (2,3-epithiopropyl) Chain aliphatic 2,3-epithiopropyloxy compounds such as oxymethyl) -3,6,9-trithiaundecane;
1,3-bis (2,3-epithiopropyloxy) cyclohexane, 1,4-bis (2,3-epithiopropyloxy) cyclohexane, 1,3-bis (2,3-epithiopropyloxymethyl) Cyclohexane, 1,4-bis (2,3-epithiopropyloxymethyl) cyclohexane, 2,5-bis (2,3-epithiopropyloxymethyl) -1,4-dithiane, 2,5-bis [[ 2- (2,3-epithiopropyloxy) ethyl] thiomethyl] -1,4-dithiane, 2,5-bis (2,3-epithiopropyloxymethyl) -2,5-dimethyl-1,4- A cycloaliphatic 2,3-epithiopropyloxy compound such as dithiane; and
1,2-bis (2,3-epithiopropyloxy) benzene, 1,3-bis (2,3-epithiopropyloxy) benzene, 1,4-bis (2,3-epithiopropyloxy) benzene 1,2-bis (2,3-epithiopropyloxymethyl) benzene, 1,3-bis (2,3-epithiopropyloxymethyl) benzene, 1,4-bis (2,3-epithiopropyl) Oxymethyl) benzene, bis [4- (2,3-epithiopropyloxy) phenyl] methane, 2,2-bis [4- (2,3-epithiopropyloxy) phenyl] propane, bis [4- ( 2,3-epithiopropyloxy) phenyl] sulfide, bis [4- (2,3-epithiopropyloxy) phenyl] sulfone, 4,4′-bis (2,3-epithiopropyloxy) Examples include aromatic 2,3-epithiopropyloxy compounds such as biphenyl, but are not limited to the exemplified compounds.

  Among these exemplified compounds, preferred compounds include bis (1,2-epithioethyl) sulfide, bis (1,2-epithioethyl) disulfide, bis (2,3-epithiopropyl) sulfide, and bis (2,3-epithio). Propylthio) methane and bis (2,3-epithiopropyl) disulfide, and more preferred compounds are bis (1,2-epithioethyl) sulfide, bis (1,2-epithioethyl) disulfide, bis (2,3- Epithiopropyl) sulfide and bis (2,3-epithiopropyl) disulfide. Further more preferred compounds are bis (2,3-epithiopropyl) sulfide and bis (2,3-epithiopropyl) disulfide.

  The amount of the epoxy compound and / or episulfide compound used varies depending on the structure and amount of the compound to be used, but considering the refractive index of the resulting resin, it is 25% by weight based on the total polymerizable composition of the present invention. % Or less is preferable. It is more preferably 23% by weight or less, and further preferably 20% by weight or less. Considering the hue and mechanical strength of the resulting resin, it is preferably 2.5% by weight or more. In the polymerizable composition, the content of the thiol compound, the epoxy compound and the episulfide compound with respect to the compound represented by the general formula (1) is low from the viewpoint of the refractive index, and the content of the epoxidized product is small. The content of the compound is preferably higher. Further, from the viewpoint of the resin hue, it is preferable that the content of the thiol compound is large.

  In the polymerizable composition, the total amount of the thiol compound, the epoxy compound, and the episulfide compound is, for example, 1 weight with respect to a total of 100 parts by weight of the compound represented by the general formula (1), the thiol compound, the epoxy compound, and the episulfide compound. Part to 50 parts by weight.

  Any one or both of the epoxy compound and / or episulfide compound can be used, and the amount ratio thereof is not particularly limited. It is also possible to use a plurality of different epoxy compounds that are different from each other or different episulfide compounds that are different from each other. However, in order to obtain a high refractive index resin, it is preferable to use an episulfide compound.

  In addition, when the thiol compound and the epoxy compound and / or episulfide compound are used in combination, the use amount ratio between the thiol compound and the epoxy compound and / or episulfide compound is the thiol group in the thiol compound and the epoxy compound and / or episulfide compound. The functional group ratio (SH group / (epoxy group + episulfide group)) with the epoxy group and / or episulfide group is preferably 0.7 or more from the viewpoint of the resin hue. More preferably, it is 0.9 or more and 5 or less, and more preferably 0.9 or more and 3 or less. If this functional group ratio is too small, the mechanical strength of the resulting resin may be undesirably lowered, and if it is too large, the heat resistance of the resulting resin may be undesirably decreased.

  When the polymerizable composition further contains an epoxy compound and / or an episulfide compound, the compound represented by the general formula (1) is included in the total weight of the polymerizable compound contained in the polymerizable composition of the present invention. The amount is not particularly limited, and is usually 10% by weight or more.

  Since the refractive index increasing material tends to be obtained as the content of the compound represented by the general formula (1) increases, it is preferably 30% by weight or more, more preferably 50% by weight or more. More preferably 70% by weight or more.

  However, if the content of the compound represented by the general formula (1) is too large, the content of the thiol compound and the epoxy compound and / or the episulfide compound is relatively reduced, so that the hue of the resin is improved and the mechanical strength is improved. From the viewpoint of suppressing the decrease in the content, the content of the compound represented by the general formula (1) in the polymerizable composition is preferably 95% by weight or less.

  In addition, when the thiol compound and the epoxy compound and / or episulfide compound are used in combination, the amount of the thiol compound used varies depending on the structure of the compound used and the structure and amount of the epoxy compound and / or episulfide compound. Since the compound represented by the general formula (1) gives a resin having a high refractive index, generally the addition of a thiol compound means a decrease in the refractive index of the resulting resin. Therefore, considering the refractive index of the obtained resin, it is preferably contained in an amount of 35% by weight or less based on the entire polymerizable composition of the present invention. It is more preferably 30% by weight or less, and further preferably 25% by weight or less. Considering the hue and mechanical strength of the resulting resin, it is preferably 2.5% by weight or more.

In addition, the polymerizable composition of the present invention contains the compound represented by the general formula (1) and the bluing agent as essential components, and may further contain elemental sulfur. The addition of simple sulfur to the polymerizable composition of the present invention is one of the preferred embodiments because it enables a further increase in the refractive index. At this time, you may further contain a polymerization catalyst as needed. In this case, in the compound represented by the general formula (1), m = 0 and X ₁ may be a sulfur atom.

  The elemental sulfur used in the polymerizable composition in the present invention is inorganic sulfur, and as a resin composition in the present invention or a transparent resin using the same, the purity is preferably 98%. Or more, more preferably 99% or more, still more preferably 99.5% or more. In order to increase purity, a method of removing volatile components may be preferable.

  Further, the property of the elemental sulfur is not a problem as long as it is a shape that can be dissolved in the compound represented by the general formula (1), but it is preferably a powder, and more preferably a fine powder.

  In the present invention, simple sulfur may be added to the polymerizable composition containing the compound represented by the general formula (1) and the bluing agent, for example, when a resin having a higher refractive index is obtained.

  As the amount of sulfur added in the polymerizable composition, from the viewpoint of high refractive index, if the amount of single sulfur added is too small relative to the total amount of the polymerizable composition of the present invention, the effect of improving the refractive index is small and not preferable. There is a case. Moreover, when there is too much addition amount of single-piece | unit sulfur, it may not be preferable from a turbid viewpoint. Therefore, it is preferable to use 5 wt% or more and 50 wt% or less of the elemental sulfur with respect to the total amount of the polymerizable composition of the present invention. More preferably, they are 5 weight% or more and 25 weight% or less.

  As a method for mixing elemental sulfur into the polymerizable composition of the present invention, for example, after adding elemental sulfur to the polymerizable composition containing the compound represented by the general formula (1) and the bluing agent, the mixture is stirred. In this case, it is preferable to increase the temperature as necessary. In addition, it may be added and dissolved in other polymerizable compounds and polymerization catalysts described later. All components may be mixed separately in the same vessel under stirring or in stages. After mixing, remixing may be performed in the same container.

  The polymerizable composition of the present invention may contain other polymerizable compounds other than the compound represented by the general formula (1) as long as the desired effects of the present invention are not impaired.

  Examples of the polymerizable compound include various known polymerizable monomers or polymerizable oligomers, and examples thereof include (meth) acrylic acid ester compounds, vinyl compounds, oxetane compounds, and thietane compounds.

  The content of these other polymerizable compounds in the total weight of the polymerizable compounds contained in the polymerizable composition of the present invention is not particularly limited, but usually the content of these other polymerizable compounds increases. Since the refractive index of the resin obtained tends to decrease as it goes on, it is usually 90% by weight or less, preferably 70% by weight or less, and more preferably 50% by weight from the viewpoint of obtaining a high refractive index material. % Or less, and most preferably 30% by weight or less. In addition, when another polymeric compound is contained in the polymeric composition of this invention, there is no restriction | limiting in particular also about the minimum of content of another polymeric compound.

  In the present invention, among the compounds represented by the general formula (1), a polymerization catalyst is not particularly required, and there is a compound in which a polymerization reaction proceeds in an autocatalytic manner, and therefore the polymerization catalyst is used as necessary. .

  The polymerization catalyst used as necessary in the present invention can usually be cured using a known method for polymerizing a thietane group-containing compound. The type and amount of the polymerization catalyst for obtaining the cured resin, the type and ratio of the monomer vary depending on the structure of the compound constituting the polymerizable composition, and cannot be generally limited. Are amines, phosphines, organic acids and salts thereof, esters, anhydrides, inorganic acids, quaternary ammonium salts, quaternary phosphonium salts, tertiary sulfonium salts, secondary iodonium salts, titanium alkoxides, Lewis acids, radicals Polymerization catalysts, cationic polymerization catalysts and the like are usually used.

Specific examples of the polymerization catalyst include triethylamine, tri-n-butylamine, tri-n-hexylamine, N, N-diisopropylethylamine, triethylenediamine, triphenylamine, N, N-dimethylethanolamine, N, N-diethylethanolamine. N, N-dibutylethanolamine, triethanolamine, N-ethyldiethanolamine, N, N-dimethylbenzylamine, N, N-diethylbenzylamine, tribenzylamine, N-methyldibenzylamine, N, N-dimethyl Cyclohexylamine, N, N-diethylcyclohexylamine, N, N-dimethylbutylamine, N-methyldicyclohexylamine, N, N-dicyclohexylmethylamine, N-methylmorpholine, N-isopropylmorpholine, pyri , Quinoline, N, N-dimethylaniline, N, N-diethylaniline, α-, β-, or γ-picoline, 2,2'-bipyridyl, 1,4-dimethylpiperazine, dicyandiamide, tetramethylethylenediamine, hexa Aliphatic and aromatic tertiary amines such as methylenetetramine, 1,8-diazabicyclo (5,4,0) -7-undecene, 2,4,6-tris (N, N-dimethylaminomethyl) phenol;
Trimethylphosphine, triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tribenzylphosphine, 1,2-bis (diphenylphosphino) ethane, 1,2-bis (dimethylphosphine) Fino) phosphines such as ethane;
Trihalogenoacetic acid such as trifluoroacetic acid, trichloroacetic acid, trifluoroacetic anhydride, ethyl trifluoroacetate, sodium trifluoroacetate and esters, anhydrides and salts thereof;
p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, trifluoromethanesulfonic anhydride, trihalogenomethanesulfonic acid such as ethyl trifluoromethanesulfonate, sodium trifluoromethanesulfonate, and esters, anhydrides and salts thereof;
Inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid;
Quaternary ammonium salts such as tetramethylammonium chloride, tetrabutylammonium chloride, tetrabutylammonium bromide;
Quaternary phosphonium salts such as tetramethylphosphonium chloride, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide;
Tertiary sulfonium salts such as trimethylsulfonium bromide and tributylsulfonium bromide;
Secondary iodonium salts such as diphenyliodonium bromide;
Dimethyltin dichloride, dibutyltin dichloride, dibutyltin dilaurate, dibutyltin diacetate, tetrachlorotin, dibutyltin oxide, diacetoxytetrabutyldistanoxane, zinc chloride, acetylacetone zinc, aluminum chloride, aluminum fluoride, triphenylaluminum, Titanium-based alkoxides such as acetylacetone aluminum, isopropoxide aluminum, tetrachlorotitanium and its complexes, tetraiodo titanium, dichlorotitanium diisopropoxide, titanium isopropoxide;
Calcium acetate;
Boron trifluoride, boron trifluoride diethyl ether complex, boron trifluoride piperidine complex, boron trifluoride ethylamine complex, boron trifluoride acetic acid complex, boron trifluoride phosphate complex, boron trifluoride t-butylmethyl Various complexes of boron trifluoride such as ether complex, boron trifluoride dibutyl ether complex, boron trifluoride THF (tetrahydrofuran) complex, boron trifluoride methyl sulfide complex, boron trifluoride phenol complex, and various types of boron trichloride Lewis acids such as trihalogenated boron compounds such as complexes and complexes thereof;
2,2′-azobis (2-cyclopropylpropionitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile) ), T-butylperoxy-2-ethylhexanoate, n-butyl-4,4′-bis (t-butylperoxy) valerate, t-butylperoxybenzoate, and the like; and diphenyliodonium hexa Cationic polymerization catalysts such as fluorophosphoric acid, diphenyliodonium hexafluoroarsenic acid, diphenyliodonium hexafluoroantimony, triphenylsulfonium tetrafluoroboric acid, triphenylsulfonium hexafluorophosphoric acid, triphenylsulfonium hexafluoroarsenic acid, and the like. Example combination It is not limited to things only.

  The above polymerization catalysts may be used alone or in admixture of two or more. When two or more of these polymerization catalysts having different reactivities are used in combination, the handling properties of the monomers, the optical properties of the resulting resin, the hue In some cases, transparency and optical distortion (pulse separation) may be improved.

Among the above compounds exemplified as the polymerization catalyst, preferred are organic tins such as dimethyltin dichloride, dibutyltin dichloride, dibutyltin dilaurate, dibutyltin diacetate, tetrachlorotin, dibutyltin oxide, diacetoxytetrabutyldistanoxane and the like. Compound;
Trihalogenoacetic acid such as trifluoroacetic acid, trichloroacetic acid, trifluoroacetic anhydride, ethyl trifluoroacetate, sodium trifluoroacetate and esters, anhydrides and salts thereof;
p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, trifluoromethanesulfonic anhydride, trihalogenomethanesulfonic acid such as ethyl trifluoromethanesulfonate, sodium trifluoromethanesulfonate, and esters, anhydrides and salts thereof;
Boron trifluoride, boron trifluoride diethyl ether complex, boron trifluoride piperidine complex, boron trifluoride ethylamine complex, boron trifluoride acetic acid complex, boron trifluoride phosphate complex, boron trifluoride t-butylmethyl Various complexes of boron trifluoride such as ether complexes, boron trifluoride dibutyl ether complexes, boron trifluoride THF complexes, boron trifluoride methyl sulfide complexes, boron trifluoride phenol complexes;
Lewis acids such as boron trichloride complexes such as boron trichloride complexes and complexes thereof; and 2,2′-azobis (2-cyclopropylpropionitrile), 2,2′-azobis (4-methoxy-2) , 4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), t-butylperoxy-2-ethylhexanoate, n-butyl-4,4′-bis (t- Radical polymerization catalysts such as butylperoxy) valerate and t-butylperoxybenzoate, more preferred are dimethyltin dichloride, trifluoromethanesulfonic acid and anhydrides, esters, salts and various complexes of boron trifluoride; 2,2′-azobis (2-cyclopropylpropionitrile), 2,2′-azobis (4-methoxy) 2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), t-butylperoxy-2-ethylhexanoate, n-butyl-4,4′-bis (t A radical polymerization catalyst such as -butylperoxy) valerate and t-butylperoxybenzoate.

  The addition amount of the polymerization catalyst of the polymerizable composition in the present invention is used in the range of 0.0001 wt% or more and 10 wt% or less, preferably 0.001 wt% or more and 10 wt%, based on the total weight of the polymerizable composition. It is used in the range of not more than wt%, more preferably not less than 0.01 wt% and not more than 5 wt%, most preferably not less than 0.01 wt% and not more than 1 wt%.

  By making the addition amount of the polymerization catalyst in the above range, it is possible to produce a resin that is cured more favorably, the pot life is more reliably maintained, and the transparency and optical properties of the resulting resin are further improved. Things can be obtained.

  The polymerization catalyst may be added directly to the polymerizable composition or a part of the compound, or may be added after being dissolved or dispersed in another compound, but after being dissolved or dispersed in another compound. The addition may give a preferable result. Furthermore, when a polymerization catalyst is added, preferable results may be obtained if it is carried out in a nitrogen atmosphere or a dry gas atmosphere. Furthermore, in order to further draw out the performance of the obtained resin, a preferable result may be obtained when the amount of unreacted functional groups remaining in the resin is 0.5% by weight or less based on the total weight of the resin, More preferably, it is 0.4% by weight or less.

  The polymerizable composition according to the present invention is a polymerizable composition containing the compound represented by the general formula (1) and a bluing agent.

  Further adjustment of optical properties such as refractive index and Abbe number of resin obtained by curing the polymerizable composition of the present invention, hue, light resistance and weather resistance, heat resistance, impact resistance, hardness, specific gravity, linear expansion coefficient , Adjustment of various properties such as polymerization shrinkage, water absorption, moisture absorption, chemical resistance, viscoelasticity, adjustment of transmittance and transparency, viscosity of the polymerizable composition, and other handling and handling methods of storage and transportation For the purpose of improving the resin and handling properties, such as for purification, washing, heat retention, cooling, filtration, reduced pressure treatment, and other organic compounds generally used in the polymerizable composition of the present invention. In some cases, it is preferable to perform an operation or add a known compound or the like as a stabilizer or a resin modifier for the purpose of obtaining a good resin. Examples of compounds added to improve stability such as long-term storage stability, polymerization stability, and thermal stability include compounds such as polymerization retarders, polymerization inhibitors, oxygen scavengers, and antioxidants.

  Purifying the polymerizable composition is a technique used for improving the transparency of a resin obtained by curing, improving the hue, and increasing the purity. The method for purifying the polymerizable composition containing the compound represented by the general formula (1) in the present invention may be a known method such as recrystallization, column chromatography (silica gel method, activated carbon method, ion exchange resin method). Any method such as extraction may be performed at any timing, and it is sufficient that the transparency and hue of the resin obtained by curing a composition generally obtained by purification are improved.

  The method of washing the polymerizable composition is a technique used to improve the transparency of the resin obtained by curing or to improve the hue, but when the polymerizable composition is synthesized and taken out or after the synthesis A substance that inhibits the transparency of the resin by washing with a polar and / or non-polar solvent at a timing such as after removal of the resin, for example, an inorganic salt used in synthesizing a polymerizable composition, or by-product, For example, a method of removing or reducing the amount of ammonium salt and the like can be mentioned. The solvent to be used is not limited in general depending on the polymerizable composition itself to be washed or the polarity of the solution containing the polymerizable composition, but the component to be removed can be dissolved and the polymerizable composition to be washed itself And those that are not compatible with the solution containing the polymerizable composition are preferable, and not only one type but also two or more types may be mixed and used. The components to be removed here vary depending on the purpose and application, but are preferably as small as possible. Usually, good results may be obtained when the content is 5000 ppm or less, more preferably 1000 ppm or less.

  The method of keeping, cooling, and filtering the polymerizable composition is a technique used to improve the transparency of the resin obtained by curing or to improve the hue, but it is synthesized and taken out. In general, it is performed at a timing such as at the time of extraction or after removal after synthesis. As a heat retention method, for example, when the polymerizable composition is crystallized during storage and handling becomes worse, the polymerizable composition and the resin obtained by curing the polymerizable composition are heated and dissolved within a range that does not deteriorate the performance. The method of doing is mentioned. The temperature range to be heated and the method of heating and dissolving cannot be generally limited by the structure of the compound constituting the polymerizable composition to be handled, but are usually performed at a temperature within the freezing point + 50 ° C., preferably within + 20 ° C., Examples thereof include a method of mechanically stirring with a stirrable device or a method of moving and dissolving the internal solution by bubbling with an inert gas in the composition. Cooling is usually performed for the purpose of increasing the storage stability of the polymerizable composition. For example, when the melting point of the polymerizable composition is high, the storage temperature should be considered in order to improve the handling property after crystallization. . Although the cold temperature cannot be generally limited by the structure of the compound constituting the polymerizable composition to be handled and the storage stability, the stability of the polymerizable composition containing the compound represented by the general formula (1) is usually used. Must be stored below the temperature that can be maintained.

  In addition, when the polymerizable composition in the present invention is a polymerizable composition used for optical applications, since its very high transparency is required, it is usually preferable to filter the polymerizable composition with a filter having a small pore size. The pore size of the filter used here is usually 0.05 μm or more and 10 μm or less. However, in consideration of operability and performance, it is preferably 0.05 μm or more and 5 μm or less, more preferably 0.1 μm or more and 5 μm or less. is there. When the polymerizable composition of the present invention is filtered without exception, good results are often obtained. As for the temperature at which filtration is performed, a more preferable result may be obtained if it is performed at a low temperature near the freezing point. However, when solidification proceeds during filtration, it is preferable to perform at a temperature that does not hinder the filtration operation. There is.

  The reduced pressure treatment is a technique generally used to remove a solvent, dissolved gas, and odor that lower the performance of a resin obtained by curing a polymerizable composition. Since the dissolved solvent may cause a decrease in the refractive index and heat resistance of the resin obtained in general, it should be removed as much as possible. The permissible value of the dissolved solvent cannot be generally limited depending on the structure of the compound constituting the polymerizable composition to be handled and the structure of the dissolved solvent, but is usually preferably 1% or less, more preferably 5000 ppm or less. . It is preferable to remove the dissolved gas from the viewpoint of suppressing the inhibition of the polymerization and the viewpoint of suppressing bubbles from being mixed into the resulting resin. In particular, it is preferable to remove a gas such as water vapor by bubbling with a dry gas. About a dissolved amount, it can set according to the structure of the compound which comprises a polymeric composition, the physical property and structure of dissolved gas, and a kind.

  As a method for producing the polymerizable composition of the present invention, typically, the compound represented by the general formula (1) and a bluing agent, a thiol compound as necessary, and various known polymerizable compounds as desired. In combination, and after adding the polymerization catalyst as necessary, mixing and dissolving may be mentioned.

  When the composition of the present invention is cured and molded, a stabilizer, a resin modifier, a chain extender, a cross-linking agent, and a light stabilizer represented by a HALS system are used according to the purpose, as in a known molding method. UV absorbers typified by benzotriazoles, antioxidants typified by hindered phenols, anti-coloring agents, fillers, external mold release agents typified by silicones, or acidic phosphates, quaternary ammonium salts Alternatively, various substances such as an internal mold release agent typified by a surfactant such as a quaternary phosphonium salt and an adhesion improver may be added. Here, the internal mold release agent includes those exhibiting a mold release effect among the various catalysts described above.

  The amount of each additive that can be added differs depending on the type, structure, and effect of each additive, and cannot be generally limited, but is usually 0.001 with respect to the total weight of the polymerizable composition. It is used in the range of not less than 10% by weight and preferably not more than 0.01% by weight and not more than 5% by weight.

Next, the resin in the present invention will be described.
The resin and the optical component made of the resin in the present invention are obtained by polymerizing the polymerizable composition. Moreover, the manufacturing method of resin in this invention includes the process of superposing | polymerizing the polymeric compound in this invention. As such a method, it is suitably carried out by various known methods used when producing plastic lenses, but cast polymerization is preferred in consideration of optical distortion.

  That is, the polymerizable composition of the present invention produced by the above-described method is subjected to a detreatment process under reduced pressure or filter filtration, if necessary, and then the obtained polymerizable composition is injected into a molding mold. Then, polymerization is performed by heating as necessary. In this case, it is preferable to polymerize by gradually heating from a low temperature to a high temperature.

  The molding mold described above is composed of two molds that are mirror-polished through a gasket made of polyethylene, ethylene-vinyl acetate copolymer, polyvinyl chloride, or the like. The mold is typically a combination of glass and glass, and other molds include glass and plastic plate, glass and metal plate, but are not limited thereto. The molding mold may be a mold in which two molds are fixed with a tape such as a polyester adhesive tape. As needed, you may perform well-known processing methods, such as a mold release process, with respect to a casting_mold | template.

  When performing cast polymerization, the polymerization temperature is affected by the polymerization conditions such as the type of polymerization initiator and is not limited, but is usually −50 ° C. or higher and 200 ° C. or lower, preferably −20 ° C. It is 170 degreeC or less, More preferably, it is 0 degreeC or more and 150 degrees C or less.

  The polymerization time is affected by the polymerization temperature, but is usually 0.01 hours or more and 200 hours or less, and preferably 0.05 hours or more and 100 hours or less. Moreover, it is also possible to carry out the polymerization by combining several temperatures such as constant temperature, temperature rise, and temperature drop as required.

  The polymerizable composition of the present invention can also be polymerized by irradiating an active energy ray such as an electron beam, ultraviolet ray or visible ray. In this case, a radical polymerization catalyst or a cationic polymerization catalyst that initiates polymerization by active energy rays is used as necessary.

If the heat resistance of the obtained resin is too low, problems such as thermal deformation may occur during daily use as a spectacle lens. On the other hand, if the heat resistance is too high, there may be a problem that the resin cannot be dyed, for example. In view of dyeability, the heat resistance of the obtained resin is preferably Tg of 100 ° C. or higher and 150 ° C. or lower.
Here, Tg is a temperature measured by a TMA (Thermal Mechanical Analysis) penetration method and obtained from an intersection of TMA curves, and corresponds to a thermal deformation start temperature.

  The obtained resin and the optical lens made of this resin may be annealed as necessary after curing. If necessary, surface polishing, antistatic treatment, hard coat treatment, non-reflective coating treatment, dyeing treatment, dyeing treatment, antireflection, high hardness, wear resistance improvement, antifogging or fashionability. Various known physical or chemical treatments such as light treatment (for example, photochromic lens formation treatment) may be performed.

  Moreover, the obtained resin and the optical lens made of this resin may be used with a coating layer on one side or both sides, if necessary. Hereinafter, an optical lens will be described as an example. Examples of the coating layer include a primer layer, a hard coat layer, an antireflection film layer, an antifogging coat film layer, an antifouling layer, and a water repellent layer. Each of these coating layers may be used alone, or a plurality of coating layers may be used in multiple layers. When a coating layer is applied to both sides, a similar coating layer or a different coating layer may be applied to each surface.

These coating layers may be used in combination with known additives for enhancing the performance of the lens. As an additive, specifically, an ultraviolet absorber for the purpose of protecting lenses and eyes from ultraviolet rays;
Infrared absorber for the purpose of protecting eyes from infrared rays;
Light stabilizers and antioxidants for the purpose of improving the weather resistance of lenses;
Dyes, pigments, and the like may be used for the purpose of enhancing the fashionability of the lens, and photochromic dyes, photochromic pigments, antistatic agents, and other various additives may be used. Moreover, regarding the layer to be coated by coating, various leveling agents for the purpose of improving coating properties may be used.

  The primer layer is usually formed between a hard coat layer described later and the optical lens. The primer layer is a coating layer for the purpose of improving the adhesion between the hard coat layer formed thereon and the lens, and in some cases, the impact resistance can also be improved.

  Any material can be used for the primer layer as long as it has high adhesion to the obtained optical lens. Usually, urethane resin, epoxy resin, polyester resin, melanin resin, and polyvinyl acetal are the main components. A primer composition is used. An appropriate solvent that does not affect the lens may be used for the primer composition in order to adjust the viscosity of the composition. Of course, you may use it without a solvent.

  The primer composition can be formed by either a coating method or a dry method. When using a coating method, a primer layer is formed by solidifying after applying to a lens by a known coating method such as spin coating or dip coating. When performing by a dry method, it forms by well-known dry methods, such as CVD method and a vacuum evaporation method. When forming the primer layer, the surface of the lens may be subjected to a pretreatment such as an alkali treatment, a plasma treatment, or an ultraviolet treatment as necessary for the purpose of improving adhesion.

  The hard coat layer is a coating layer for the purpose of imparting functions such as scratch resistance, abrasion resistance, moisture resistance, warm water resistance, heat resistance, and weather resistance to the lens surface.

  The hard coat layer is generally selected from a curable organosilicon compound and an element group of Si, Al, Sn, Sb, Ta, Ce, La, Fe, Zn, W, Zr, In, and Ti. A hard coat composition containing fine particles composed of oxide fine particles containing one kind of element and / or a composite oxide of two or more kinds of elements selected from these element groups is used. One kind of fine particles composed of oxide fine particles and / or composite oxides may be used in the hard coat composition, or two or more kinds may be used in combination.

  In addition to the above components, the hard coat composition includes amines, amino acids, metal acetylacetonate complexes, organic acid metal salts, perchloric acids, perchloric acid salts, acids, metal chlorides and polyfunctional epoxy compounds. It is preferable to include at least one of them. An appropriate solvent that does not affect the lens may be used in the hard coat composition. Of course, you may use it without a solvent.

  The hard coat layer is usually formed by applying a hard coat composition by a known application method such as spin coating or dip coating, followed by curing. Examples of the curing method include thermal curing, a curing method by irradiation with energy rays such as ultraviolet rays and visible rays, and the like. In order to suppress the occurrence of interference fringes, the refractive index of the hard coat layer is preferably such that the difference in refractive index from the lens is within a range of ± 0.1 (plus or minus).

The antireflection layer is usually formed on the hard coat layer as necessary. There are inorganic and organic antireflection layers. In the case of inorganic systems, inorganic oxides such as SiO ₂ and TiO ₂ are used, and vacuum deposition, sputtering, ion plating, ion beam assist, and CVD are used. It is formed by the dry method. In the case of an organic type, it is formed by a wet method using a composition containing an organosilicon compound and silica-based fine particles having internal cavities.

The antireflection layer includes a single layer and a multilayer, and when used in a single layer, the refractive index is preferably at least 0.1 lower than the refractive index of the hard coat layer. In order to exhibit the antireflection function more effectively, a multilayer antireflection film is preferable. In that case, a low refractive index film and a high refractive index film are alternately laminated. Also in this case, the refractive index difference between the low refractive index film and the high refractive index film is preferably 0.1 or more. Examples of the high refractive index film include ZnO, TiO ₂ , CeO ₂ , Sb ₂ O ₅ , SnO ₂ , ZrO ₂ , and Ta ₂ O _5, and examples of the low refractive index film include an SiO ₂ film. .

  On the antireflection film layer, an antifogging coating film layer, a contamination prevention layer, and a water repellent layer may be formed as necessary. As a method for forming the antifogging coat layer, the antifouling layer, and the water repellent layer, there is no particular limitation on the treatment method, treatment material, and the like as long as the antireflection function is not adversely affected. A coating treatment method, antifouling treatment method, water repellent treatment method, and material can be used.

  For example, in the anti-fogging coat and anti-fouling treatment method, a method of covering the surface with a surfactant, a method of adding a hydrophilic film to the surface to make it water-absorbing, a method of covering the surface with fine irregularities and increasing water absorption, Examples thereof include a method of absorbing water using photocatalytic activity and a method of preventing water droplet adhesion by applying a super water-repellent treatment.

  Further, in the water repellent treatment method, a method of forming a water repellent treatment layer by vapor deposition or sputtering of a fluorine-containing silane compound or the like, or a method of forming a water repellent treatment layer by coating after dissolving the fluorine-containing silane compound in a solvent Etc.

  The cured resin and optical component obtained by polymerizing the polymerizable composition of the present invention are excellent in transparency, reduced in yellowness, and have a high refractive index exceeding a refractive index (ne) of 1.7. is doing.

Examples of the optical component in the present invention include various plastic lenses such as eyeglass lenses for correcting vision, lenses for imaging devices, Fresnel lenses for liquid crystal projectors, lenticular lenses, and contact lenses;
Sealing material for light emitting diode (LED);
Optical waveguide;
Optical adhesive used for bonding optical lenses and optical waveguides;
Anti-reflective film used for optical lenses;
Examples thereof include a transparent coating or a transparent substrate used for liquid crystal display device members such as a substrate, a light guide plate, a film and a sheet.

  Thus, the resin obtained by polymerizing the polymerizable compound of the present invention has high transparency, good heat resistance and mechanical strength, and a high refractive index exceeding a refractive index (ne) of 1.7. For example, it is useful as a resin used for optical parts such as plastic lenses. Moreover, the polymerizable composition of the present invention is useful as a raw material monomer composition for a transparent resin having a very high refractive index, for example.

Hereinafter, the present invention will be described more specifically with reference to production examples and examples, but the present invention is not limited to these examples.
In the following examples, the glass transition temperature (Tg) is a temperature measured by the TMA penetration method and obtained from the intersection of the TMA curves, and corresponds to the thermal deformation start temperature.

(Reference Production Example 1)
According to the method described in Patent Document 3 (Japanese Patent Laid-Open No. 2003-327583), 3-thiethanol was synthesized.

  Further, 3-mercaptothietane was synthesized using the obtained 3-thiethanol. That is, in a reactor equipped with a stirrer and a thermometer, 190 g of thiourea, 253 g of 35% hydrochloric acid water and 250 g of water were charged and stirred, and 156 g of 3-thiethanol was added over 1 hour. Appropriate. After reacting by stirring at 30 ° C. for 24 hours, 177 g of 24% aqueous ammonia was appropriately reduced over 1 hour. Furthermore, after reacting at 30 degreeC for 15 hours, it stood still and the organic layer (lower layer) was taken out, and 134 g of crude products were obtained. The obtained crude product was distilled under reduced pressure, and fractions having a boiling point of 40 ° C./106 Pa were collected to obtain 3-mercaptothietane, which was a colorless transparent liquid target product.

(Reference Production Example 2)
(Production of the compound represented by CMPD. (Compound) No. 1-1 in Table 1 above)
11.15 g (0.105 mol) of 3-mercaptothietane was charged in 50 g of pure water, followed by dropwise addition of 41.2 g (0.103 mol) of 10% NaOH aqueous solution at room temperature over 40 minutes. I entered. Subsequently, the temperature of the reaction solution was raised to 30 ° C., and 65.2 g of a 10% tin tetrachloride aqueous solution (corresponding to 0.025 mol of tin tetrachloride) was added dropwise at the same temperature over 4 hours. After completion of dropping, the mixture was further stirred at the same temperature for 2 hours. To this reaction mixture, 100 ml of chloroform was added, and the mixture was separated into an organic layer and an aqueous layer. The organic layer was washed twice with 100 ml of pure water and then dried using anhydrous sodium sulfate. The solvent was distilled off from this extract, and in Table 1, CMPD. No. 13.40 g (99% yield) of the compound represented by 1-1 was obtained.

(Preparation of polymerizable composition and production of cured resin by polymerization)
The physical properties of the resins or optical components (lenses) produced in the following Examples and Comparative Examples were evaluated for Examples 1 to 4 and Comparative Examples 1 to 3 by the following method.
Appearance: The presence of transparency and optical distortion was confirmed by visual observation and microscopic observation.
Refractive index: Measured at 20 ° C. using a Purfrich refractometer.
Hue: Based on ASTM D1925, the yellowness (YI) of a 2 mm thick flat plate was measured using a spectrophotometer CE-7000A manufactured by Greta Macbeth.

(Example 1)
In advance, CMPD. No. 1-1 mg of “PS Violet RC” (trade name of Dystar Japan) was dissolved in 50 g of the compound represented by 1-1, and CMPD. No. A solution of the compound represented by 1-1 was prepared (conditioning liquid A).

  In Table 1 produced in Reference Production Example 2 in a glass beaker at 40 ° C., CMPD. No. 90 parts by weight of the compound represented by 1-1 and 10 parts by weight of the adjustment liquid A were weighed and adjusted so that 10 ppm of the bluing agent was contained in the monomer. After filtration through a Teflon (registered trademark) filter without adding a polymerization catalyst, the mixture was sufficiently deaerated until no foaming was observed under a reduced pressure of 1.3 kPa or less. After injecting the degassable polymerizable composition into a mold composed of a glass mold and a tape, it was placed in a heating oven and polymerized for 20 hours. During the polymerization, the temperature in the oven was increased from 60 ° C. to 120 ° C. in multiple stages.

  The obtained resin molded piece had good transparency and good appearance without distortion. Regarding the hue, the yellowness was 6.

(Example 2)
In advance, 5 mg of “PS Violet RC” (trade name of Dystar Japan) is dissolved in 50 g of 3-mercaptothietane to prepare a 3-mercaptothietane solution having a bluing agent concentration of 100 ppm. Oita (conditioning liquid B).

  In Table 1 produced in Reference Production Example 2 in a glass beaker at 40 ° C., CMPD. No. 95 parts by weight of the compound represented by 1-1 and 5 parts by weight of the adjustment liquid B were weighed and adjusted so that 5 ppm of the bluing agent was contained in the monomer. After filtration through a Teflon (registered trademark) filter without adding a polymerization catalyst, the mixture was sufficiently deaerated until no foaming was observed under a reduced pressure of 1.3 kPa or less. After injecting the degassable polymerizable composition into a mold composed of a glass mold and a tape, it was placed in a heating oven and polymerized for 20 hours. During the polymerization, the temperature in the oven was increased from 60 ° C. to 120 ° C. in multiple stages.

  The obtained resin molded piece had good transparency and good appearance without distortion. As for the hue, the yellowness was 5.

(Example 3)
In advance, 5 mg of “PS Violet RC” (trade name of Dystar Japan) as a bluing agent was dissolved in 50 g of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, and the concentration of bluing agent was 100 ppm. Of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (Preparation solution C).

  In Table 1 produced in Reference Production Example 2 in a glass beaker at 40 ° C., CMPD. No. 1-1. 52.5 parts by weight of the compound represented by 1-1, 2 parts by weight of the adjustment liquid C, and 5.5 parts by weight of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane were weighed and added to the monomer. It was adjusted to contain 2 ppm of bluing agent. After filtration through a Teflon (registered trademark) filter without adding a polymerization catalyst, the mixture was sufficiently deaerated until no foaming was observed under a reduced pressure of 1.3 kPa or less. After injecting the degassable polymerizable composition into a mold composed of a glass mold and a tape, it was placed in a heating oven and polymerized for 20 hours. During the polymerization, the temperature in the oven was increased from 60 ° C. to 120 ° C. in multiple stages.

  The obtained resin molded piece had good transparency and good appearance without distortion. As for the hue, the yellowness was 1.

(Example 4)
In advance, 5 mg of “PS Blue RR” (trade name of Dystar Japan) was dissolved in 50 g of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane as a bluing agent, and the concentration of bluing agent was 100 ppm. Of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (Preparation solution D).

  In Table 1 produced in Reference Production Example 2 in a glass beaker at 40 ° C., CMPD. No. 12.5 parts by weight of the compound represented by 1-1, 2 parts by weight of the adjustment liquid D, and 5.5 parts by weight of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane were weighed and added to the monomer. It was adjusted to contain 2 ppm of bluing agent. After filtration through a Teflon (registered trademark) filter without adding a polymerization catalyst, the mixture was sufficiently deaerated until no foaming was observed under a reduced pressure of 1.3 kPa or less. After injecting the degassable polymerizable composition into a mold composed of a glass mold and a tape, it was placed in a heating oven and polymerized for 20 hours. During the polymerization, the temperature in the oven was increased from 60 ° C. to 120 ° C. in multiple stages.

  The obtained resin molded piece had good transparency and good appearance without distortion. As for the hue, the yellowness was 4.

(Comparative Example 1)
In Table 1 produced in Reference Production Example 2 in a glass beaker at 40 ° C., CMPD. No. 100 parts by weight of the compound represented by 1-1 was weighed. After filtration through a Teflon (registered trademark) filter without adding a polymerization catalyst, the mixture was sufficiently deaerated until no foaming was observed under a reduced pressure of 1.3 kPa or less. After injecting the degassable polymerizable composition into a mold composed of a glass mold and a tape, it was placed in a heating oven and polymerized for 20 hours. During the polymerization, the temperature in the oven was increased from 60 ° C. to 120 ° C. in multiple stages.

  The obtained resin molded piece had good transparency and good appearance without distortion. As for the hue, it was colored yellow as compared with the case where the yellowness level 38 and the bluing agent were added.

(Comparative Example 2)
In Table 1 produced in Reference Production Example 2 in a glass beaker at 40 ° C., CMPD. No. 95 parts by weight of the compound represented by 1-1 and 5 parts by weight of 3-mercaptothietane as a thiol compound were weighed. After filtration through a Teflon (registered trademark) filter without adding a polymerization catalyst, the mixture was sufficiently deaerated until no foaming was observed under a reduced pressure of 1.3 kPa or less. After injecting the degassable polymerizable composition into a mold composed of a glass mold and a tape, it was placed in a heating oven and polymerized for 20 hours. During the polymerization, the temperature in the oven was increased from 60 ° C. to 120 ° C. in multiple stages.

  The molded piece of the obtained resin had good transparency and good appearance without distortion, but the hue was colored yellow compared to the one with a yellowness of 12 and a bluing agent. .

(Comparative Example 3)
In Table 1 produced in Reference Production Example 2 in a glass beaker at 40 ° C., CMPD. No. 92.5 parts by weight of the compound represented by 1-1 and 7.5 parts by weight of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane as a thiol compound were weighed. After filtration through a Teflon (registered trademark) filter without adding a polymerization catalyst, the mixture was sufficiently deaerated until no foaming was observed under a reduced pressure of 1.3 kPa or less. After injecting the degassable polymerizable composition into a mold composed of a glass mold and a tape, it was placed in a heating oven and polymerized for 20 hours. During the polymerization, the temperature in the oven was increased from 60 ° C. to 120 ° C. in multiple stages.

  The resulting resin molded piece had good transparency and good appearance without distortion, but the hue was 6 compared to that containing a yellowing degree 6 and a bluing agent (Example 4), It was colored yellow.

The optical properties (refractive index, Abbe number), heat resistance, and hue of the resins produced in Examples 5 to 9 and Comparative Examples 4 and 5 were evaluated by the following test methods.
Refractive index (ne) and Abbe number (νe): Measured at 20 ° C. using a Purfrich refractometer.
Heat resistance: Tg (° C.) in the TMA penetration method (50 g load, pin tip 0.5 mmφ, heating rate 10 ° C./min) was defined as heat resistance.
Hue: The resin hue YI value was measured using a color difference meter (CR-200) manufactured by Minolta. The resin hue YI value was measured by preparing a flat plate having a thickness of 3 mm.

(Example 5)
In advance, 40 mg of “PS Violet RC” (trade name of Dystar Japan), which is a violet dye as a bluing agent, is dissolved in 50 g of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, A 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane solution having a blueing agent concentration of 800 ppm was prepared (conditioning solution E).

  CMPD. No. 1-1, 85 parts by weight of the compound represented by 1-1, 0.13 parts by weight of Preparation E, 4.87 parts by weight of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, and 3-mercaptothie Ten parts by weight of tan was weighed out and adjusted so that 1 ppm of the bluing agent was contained in the monomer. N-methyldicyclohexylamine was added thereto so as to have a total concentration of 380 ppm, and stirred under heating to obtain a uniform solution. Next, after filtration through a PTFA filter, the mixture was sufficiently deaerated under a reduced pressure of 3.9 kPa or less until no foaming was observed. The polymerizable composition after degassing was poured into a mold composed of a glass mold and a tape, and then placed in a heating oven for polymerization for 46 hours. During the polymerization, the temperature in the oven was increased from 70 ° C. to 130 ° C. in multiple stages.

  The obtained resin molded piece had good transparency and good appearance without distortion. The refractive index (ne) was 1.779, and the Abbe number (νe) was 26.4. Tg was 105 ° C. The hue was as good as YI = 5.2.

(Example 6)
In advance, 50 mg of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 20 mg of “PS Violet RC” which is a violet dye as a bluing agent and “MLP Red V-1” which is a red dye ( 20 mg of Dystar Japan Co., Ltd.) was dissolved, and a 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane solution having a bluing agent concentration of 800 ppm was prepared (conditioning solution F).

  CMPD. No. 85 parts by weight of the compound represented by 1-1, 0.25 parts by weight of the adjustment liquid F, 4.75 parts by weight of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, and 3-mercaptothie Ten parts by weight of tan were weighed out and adjusted so that 2 ppm of the bluing agent was contained in the monomer. N-methyldicyclohexylamine was added thereto so as to have a total concentration of 380 ppm, and stirred under heating to obtain a uniform solution. Next, after filtration through a PTFA filter, the mixture was sufficiently deaerated under a reduced pressure of 3.9 kPa or less until no foaming was observed. The polymerizable composition after degassing was poured into a mold composed of a glass mold and a tape, and then placed in a heating oven for polymerization for 46 hours. During the polymerization, the temperature in the oven was increased from 70 ° C. to 130 ° C. in multiple stages.

  The obtained resin molded piece had good transparency and good appearance without distortion. The refractive index (ne) was 1.777, and the Abbe number (νe) was 26.6. Tg was 107 ° C. The hue was as good as YI = 5.1.

(Example 7)
CMPD. No. 1-11, 85 parts by weight of the compound represented by 1-1, 0.19 parts by weight of the adjustment solution F prepared in Example 6, and 4.81 parts by weight of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane And 10 parts by weight of 3-mercaptothietane were weighed and adjusted so that 1.5 ppm of the bluing agent was contained in the monomer. N-methyldicyclohexylamine was added thereto so as to have a total concentration of 380 ppm, and stirred under heating to obtain a uniform solution. Next, after filtration through a PTFA filter, the mixture was sufficiently deaerated under a reduced pressure of 3.9 kPa or less until no foaming was observed. The polymerizable composition after degassing was poured into a mold composed of a glass mold and a tape, and then placed in a heating oven for polymerization for 46 hours. During the polymerization, the temperature in the oven was increased from 70 ° C. to 130 ° C. in multiple stages.

  The obtained resin molded piece had good transparency and good appearance without distortion. The refractive index (ne) was 1.777, and the Abbe number (νe) was 26.5. Tg was 104 ° C. The hue was as good as YI = 7.4.

(Example 8)
CMPD. No. 1-11, 85 parts by weight of the compound represented by 1-1, 0.31 part by weight of the adjustment solution F prepared in Example 6, and 4.69 parts by weight of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane And 10 parts by weight of 3-mercaptothietane were weighed and adjusted so that 2.5 ppm of the bluing agent was contained in the monomer. N-methyldicyclohexylamine was added thereto so as to have a total concentration of 380 ppm, and stirred under heating to obtain a uniform solution. Next, after filtration through a PTFA filter, the mixture was sufficiently deaerated under a reduced pressure of 3.9 kPa or less until no foaming was observed. The polymerizable composition after degassing was poured into a mold composed of a glass mold and a tape, and then placed in a heating oven for polymerization for 46 hours. During the polymerization, the temperature in the oven was increased from 70 ° C. to 130 ° C. in multiple stages.

  The obtained resin molded piece had good transparency and good appearance without distortion. The refractive index (ne) was 1.779, and the Abbe number (νe) was 26.4. Tg was 106 ° C. The hue was as good as YI = 5.2.

Example 9
In advance, 100 mg of bis (2,3-epithiopropyl) disulfide, 5 mg of violet dye “PS Violet RC” as a bluing agent and “MLP Red V-1”, a red dye (product of Dystar Japan) Name) 5 mg was dissolved and a bis (2,3-epithiopropyl) disulfide solution having a bluing agent concentration of 100 ppm was prepared (conditioning solution G).

  CMPD. No. 86 parts by weight of the compound represented by 1-1, 3 parts by weight of the adjustment liquid G, 4 parts by weight of bis (2,3-epithiopropyl) disulfide, and 7 parts by weight of 3-mercaptothietane at 75 ° C. After heating and mixing and dissolving under reduced pressure with a PTFA filter, the mixture was sufficiently deaerated until no foaming was observed under a reduced pressure of 3.9 kPa or less. Subsequently, the degassable polymerizable composition was poured into a mold composed of a glass mold and a tape, and then placed in a heating oven for polymerization for 46 hours. During the polymerization, the temperature in the oven was increased from 70 ° C. to 130 ° C. in multiple stages.

  The obtained resin molded piece had good transparency and good appearance without distortion. The refractive index (ne) was 1.786, and the Abbe number (νe) was 25.5. Tg was 140 ° C. As for the hue, YI = 7.0 was favorable.

(Comparative Example 4)
CMPD. No. 85 parts by weight of the compound represented by 1-1, 10 parts by weight of 3-mercaptothietane, and 5 parts by weight of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane were weighed. N-methyldicyclohexylamine was added thereto so as to have a total concentration of 380 ppm, and stirred under heating to obtain a uniform solution. Next, after filtration through a PTFA filter, the mixture was sufficiently deaerated under a reduced pressure of 3.9 kPa or less until no foaming was observed. The polymerizable composition after degassing was poured into a mold composed of a glass mold and a tape, and then placed in a heating oven for polymerization for 46 hours. During the polymerization, the temperature in the oven was increased from 70 ° C. to 130 ° C. in multiple stages.

  The obtained resin molded piece had good transparency and good appearance without distortion. The refractive index (ne) was 1.780, and the Abbe number (νe) was 26.3. Tg was 105 ° C. As for the hue, YI = 12, it was colored yellow compared with the one containing the bluing agent.

(Comparative Example 5)
CMPD. No. 86 parts by weight of the compound represented by 1-1, 7 parts by weight of 3-mercaptothietane as the thiol compound, and 7 parts by weight of bis (2,3-epithiopropyl) disulfide as the episulfide compound are mixed by heating at 75 ° C. The mixture was filtered under reduced pressure with a PTFA filter, and then sufficiently deaerated until no foaming was observed under a reduced pressure of 3.9 kPa or less. Subsequently, the degassable polymerizable composition was poured into a mold composed of a glass mold and a tape, and then placed in a heating oven for polymerization for 46 hours. During the polymerization, the temperature in the oven was increased from 70 ° C. to 130 ° C. in multiple stages.

  The obtained resin molded piece had good transparency and good appearance without distortion. The refractive index (ne) was 1.785, and the Abbe number (νe) was 25.7. Tg was 143 ° C. As for the hue, YI = 22, which was colored yellow as compared with the one containing the bluing agent.

Claims (20)

A polymerizable composition comprising one or more thietane groups and a metal atom in the molecule, a compound represented by the following general formula (1), and a bluing agent.

(In the general formula (1), M represents a metal atom, X ₁ and X ₂ each independently represents a sulfur atom or an oxygen atom, R ₁ represents a divalent organic group, and m represents 0 or 1) When p represents an integer of 1 to n, n represents a valence of the metal atom M, Y represents each independently an inorganic or organic residue, and np is 2 or more, Y may be bonded to each other to form a ring containing a metal atom M.)   The polymerizable composition according to claim 1, further comprising a thiol compound.   The polymerizable composition according to claim 2, further comprising an epoxy compound and / or an episulfide compound. The polymerizable composition according to claim 3,
The total of the thiol compound, the epoxy compound and the episulfide compound is from 1 part by weight to 50 parts by weight with respect to the total of 100 parts by weight of the compound represented by the general formula (1), the thiol compound, the epoxy compound and the episulfide compound. A polymerizable composition.   The polymerizable composition according to claim 1, wherein the bluing agent is a dye.   The polymerizable composition according to claim 5, wherein the bluing agent is a dye containing one or more dyes selected from blue dyes and violet dyes.   The polymerizable composition according to claim 6, wherein the content of the bluing agent is in the range of 0.001 ppm to 500 ppm with respect to the total weight of the polymerizable compounds contained in the polymerizable composition. Polymerizable composition.   The polymerizable composition according to claim 1, wherein the metal atom is any one of Group 4, Group 8, Group 10, Group 11, Group 12, Group 13, Group 14 and Group 15 of the long-period periodic table. A polymerizable composition.   The polymerizable composition according to claim 8, wherein the metal atom is any one of Group 4, 12, 13, and 14 of the long-period periodic table.   The polymerizable composition according to claim 9, wherein the metal atom is a Sn atom.   The polymerizable composition according to claim 1, wherein m = 0. The polymerizable composition according to claim 11, wherein X ₁ is a sulfur atom.   The polymerizable composition according to claim 12, wherein n = p.   The polymerizable composition according to claim 13, wherein the metal atom is a Sn atom.   The polymerizable composition according to claim 14, further comprising a thiol compound.   The polymerizable composition according to claim 15, further comprising an epoxy compound and / or an episulfide compound.   A method for producing a resin, comprising a step of cast polymerization of the polymerizable composition according to claim 1.   A resin obtained by polymerizing the polymerizable composition according to claim 1.   An optical component comprising the resin according to claim 18.   A lens made of the resin according to claim 18.